CN114605712B - Pre-polymerized liquid, biocompatible conductive hydrogel and preparation method thereof - Google Patents

Pre-polymerized liquid, biocompatible conductive hydrogel and preparation method thereof Download PDF

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CN114605712B
CN114605712B CN202011448568.1A CN202011448568A CN114605712B CN 114605712 B CN114605712 B CN 114605712B CN 202011448568 A CN202011448568 A CN 202011448568A CN 114605712 B CN114605712 B CN 114605712B
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conductive hydrogel
biocompatible conductive
gel
monomer
concentration
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CN114605712A (en
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韦华
陈静
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Ningbo Institute of Material Technology and Engineering of CAS
Cixi Institute of Biomedical Engineering CIBE of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
Cixi Institute of Biomedical Engineering CIBE of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

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Abstract

The application discloses a prepolymerization solution, a biocompatible conductive hydrogel, and a preparation method and application thereof. A pre-polymerization liquid, which contains natural polysaccharide, a zwitterionic monomer, a hydroxyalkyl methacrylate monomer, an ethylenediamine tetraacetic acid metal complex and an initiator. And adding protonic acid into the prepolymerization solution to complex the natural polysaccharide, and then photoinitiating to carry out curing polymerization to obtain the biocompatible conductive hydrogel. The biocompatible conductive hydrogel has the advantages of ultra-high stretchability, transparency, self-adhesion and biocompatibility, and has wide application in the technical fields of biomedical high polymer materials and flexible electronics.

Description

Pre-polymerized liquid, biocompatible conductive hydrogel and preparation method thereof
Technical Field
The application relates to a preparation method and application of biocompatible conductive hydrogel, and belongs to the technical fields of biomedical high polymer materials and flexible electronics.
Background
The skin has the functions of softening, self-repairing and protecting viscera from injury, and can sense changes of external pressure, temperature, humidity and the like. In recent years, research on wearable electronic devices and electronic skin materials has been promoted, and the wearable electronic devices and electronic skin materials are widely applied to the fields of biomedicine, soft robots, artificial limbs, health monitoring and the like. Conventional strain sensors use metal as a substrate to achieve signal transduction by electron transfer, but the strain of the material is small. Although the conductive material can be prepared by compounding a semiconductor, graphene, or the like with an elastomer, stretching breaks the contact state of the conductor and the base material, gaps occur, and sensitivity is lowered. In order to obtain an ideal sensor, the material is required to have mechanical flexibility, stretchability, conductivity and self-adhesion, and the external stimulus is accurately converted into an electric signal. Hydrogel, which is a three-dimensional network polymer containing water, generally has the characteristics of biocompatibility, flexibility, high stretchability and the like, and is widely applied to the fields of tissue engineering, drug release control, flexible electronics and the like based on the unique structure and inherent flexibility thereof.
Because the transmission of signals in human bodies is ionic electric signals, developing an ionic conductive hydrogel which can not only meet the stretchability but also simulate the transmission of bioelectric signals is particularly important in the field of wearable electronic devices. In addition, the modulus of the material and the modulus of biological tissue (10 4 -10 9 Pa) is similar, the viscoelastic behaviour of the skin can be well simulated. The fit between the strain sensor and the substrate is the key to accurately capturing signals, so that the self-adhesion performance is also increasingly emphasized in application; at the same time the transparency of the material is also important for the immediate observation of the skin condition. At present, the ion conductive hydrogel applied to the field still has the problems of difficult optimization of conductivity and mechanical property, lack of self-adhesion property, poor transparency, single functionalization and the like. This has limited the use of hydrogels in the field of flexible wearable electronics.
Disclosure of Invention
The invention aims to provide a natural polysaccharide-based high-tensile, transparent and tissue-adhesive biocompatible conductive hydrogel and a multiple strain sensor based on the material.
The ion-conductive hydrogel is a semi-interpenetrating network hydrogel based on non-covalent interaction, takes natural polysaccharide sodium alginate as a framework material, and generates H by utilizing hydrolysis of glucono-lactone (GDL) + Triggering disodium calcium ethylenediamine tetraacetate (EDTANa) 2 Ca) releases calcium ions to obtain the calcium alginate ion complexing network with a slow release system. Then combining the zwitterionic monomer with adhesive propertiesThe hydroxyalkyl methacrylate monomer penetrates through the polysaccharide network, and a cross-linking agent is not added for in-situ copolymerization to obtain the semi-interpenetrating network hydrogel based on non-covalent interaction. The polyamphoterion chains have stronger electrostatic interaction with each other, so that an electrostatic interaction network is formed, the ion transmission speed in the system is improved, and the gel has better conductive performance. Sodium alginate is taken as a polysaccharide macromolecular framework, contains negative charge groups, can form interpenetrating networks with amphoteric ions, and can enhance gel and endow the gel with good water retention performance. The gel contains a large amount of hydrogen bonds and electrostatic action, and the synergistic effect of the two gives the gel super-strong adhesiveness.
According to a first aspect of the present application, a prepolymerization solution is provided.
A pre-polymerization liquid, which contains natural polysaccharide, a zwitterionic monomer, a hydroxyalkyl methacrylate monomer, an ethylenediamine tetraacetic acid metal complex and an initiator.
Optionally, the concentration of the natural polysaccharide in the prepolymer solution is 1-5 wt%.
Alternatively, the concentration of the zwitterionic monomer is from 0.5 to 3mol/L.
Alternatively, the concentration of the hydroxyalkyl methacrylate monomer is 1 to 3mol/L.
Alternatively, the concentration of the metal complex of ethylenediamine tetraacetic acid is 0.1 to 0.5mol/L.
Alternatively, the initiator concentration is 0.1 to 0.5mol/L.
Alternatively, the concentration of the natural polysaccharide is independently selected from any value or range of values between any two of 1wt%, 2wt%, 3wt%, 4wt%, 5wt%.
Alternatively, the concentration of the zwitterionic monomer is independently selected from any value or range of values between any two of 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L.
Alternatively, the concentration of the hydroxyalkyl methacrylate monomer is independently selected from any of 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, or a range of values between any two.
Alternatively, the concentration of the metal complex of ethylenediamine tetraacetic acid is independently selected from any of 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, or a range of values between any two.
Alternatively, the concentration of initiator is independently selected from any value or range of values between any two of 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L.
Optionally, the metal complex of ethylenediamine tetraacetic acid is at least one selected from disodium calcium ethylenediamine tetraacetate and disodium iron ethylenediamine tetraacetate.
Optionally, the natural polysaccharide comprises at least one of sodium alginate, carrageenan, hyaluronic acid and chitosan.
Optionally, the zwitterionic monomer is selected from at least one of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium, N-dimethylaminopropyl triethoxysilane sulfonate inner salt, N-cyclohexyl-3-aminopropanesulfonic acid and polyacetaine type.
Optionally, the polyacid betaine type is selected from at least one of a polycarboxylic acid betaine type, a polysulfonic acid betaine type, and a polyphosphoric acid betaine type.
Specifically, the polysulfonate betaine is vinylimidazole sulfonate betaine.
Optionally, the hydroxyalkyl methacrylate monomer is at least one selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate.
Optionally, the initiator is a water-soluble photoinitiator.
Optionally, the water-soluble photoinitiator is selected from at least one of 1173, quant acid BTC, quant acid BPQ.
According to a second aspect of the present application, a method of preparing a prepolymer solution is provided.
A process for preparing the prepolymer liquid includes such steps as dissolving natural polyose in water, adding zwitterionic monomer, hydroxyalkyl methacrylate monomer, ethylenediamine tetraacetic acid metal complex and trigger, light-shielding treatment and stirring.
According to a third aspect of the present application, a method of preparing a biocompatible conductive hydrogel is provided.
The preparation method of the biocompatible conductive hydrogel comprises the steps of adding protonic acid into a prepolymerization solution to complex natural polysaccharide, and then photoinitiating to carry out curing polymerization to obtain the biocompatible conductive hydrogel;
the pre-polymerization liquid is at least one selected from the pre-polymerization liquid and the pre-polymerization liquid obtained by the preparation method.
Optionally, the protonic acid is at least one selected from glucono-lactone, oxalic acid and gluconic acid.
Optionally, the concentration of the protonic acid in the prepolymer solution is 0.1-0.5 mol/L.
Alternatively, the concentration of the protonic acid is independently selected from any of 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, or a range of values between any two.
Optionally, the complexing time is 0.5-4 h.
Optionally, the photoinitiation is ultraviolet light initiation.
In the application, the ultraviolet light initiation condition is that the power is 8W, and the ultraviolet light with the wavelength of 365nm irradiates for 2-3 hours.
Optionally, adding glucono-lactone into a prepolymerization solution containing sodium alginate, a zwitterionic monomer, disodium calcium ethylenediamine tetraacetate and an initiator to complex the sodium alginate, and then photoinitiating to carry out curing polymerization to obtain the ion-conductive hydrogel.
Sodium alginate has the advantage of being capable of chelating multivalent ions to form complexation rapidly, but has large rigidity of a complexation structure, cannot form effective entanglement, and has poor mechanical properties. Therefore, by adding a monomer into a sodium alginate system or adjusting a crosslinking mode, intermolecular/intramolecular interaction is improved, a double-network hydrogel is constructed, and mechanical properties are improved.
Optionally, the method comprises:
(1) Dissolving natural polysaccharide in water, adding a zwitterionic monomer, a hydroxyalkyl methacrylate monomer, an ethylenediamine tetraacetic acid metal complex and an initiator, and mixing uniformly in a dark place to obtain a prepolymer;
(2) Adding protonic acid, stirring uniformly, injecting into a mold, and releasing metal ions in the ethylenediamine tetraacetic acid metal complex to completely complex the natural polysaccharide;
(3) When photoinitiated curing polymerization is adopted, the biocompatible conductive hydrogel is obtained by irradiating for 2-3 hours under ultraviolet light with the power of 8W and the wavelength of 365 nm.
Optionally, the method comprises:
(1) Dissolving sodium alginate in water, adding a zwitterionic monomer, a hydroxyalkyl methacrylate monomer, disodium calcium ethylenediamine tetraacetate and an initiator, and mixing uniformly in a dark place to obtain a prepolymer;
(2) Adding glucono-lactone, stirring, and pouring into a mold to obtain EDTANa 2 Ca in Ca 2+ Releasing to completely complex sodium alginate;
(3) When photoinitiated curing polymerization is adopted, the ion conductive hydrogel is obtained by irradiating for 2 to 3 hours under ultraviolet light with the power of 8W and the wavelength of 365 nm.
According to another aspect of the present application, there is provided the biocompatible conductive hydrogel prepared by the preparation method described above.
Optionally, the biocompatible conductive hydrogel has a breaking stress of 1.01-8.97KPa.
Optionally, the biocompatible conductive hydrogel has an elongation at break of 254-1288%.
Alternatively, the compressive strain of the biocompatible conductive hydrogel is between 0.56 and 6.02MPa at 98%.
Optionally, the biocompatible conductive hydrogel has an adhesion to pigskin of 4.3 to 21Pa.
Optionally, the conductivity of the biocompatible conductive hydrogel is 0.16-0.732S/m. Optionally, the biocompatible conductive hydrogel has a light transmittance of 75% -97%.
According to still another aspect of the application, the application of the biocompatible conductive hydrogel prepared by the preparation method in a multiple strain sensor and ion skin is provided.
The biocompatible conductive hydrogel has the advantages of ultra-high stretchability, transparency, self-adhesion and biocompatibility, the network deformation of the ion conductive hydrogel under the action of stress shows resistance change, and the change of ion movement speed under the condition of temperature change also leads to resistance change, namely strain induction, so that the multi-sensing of strain temperature is realized.
In the present application, "EDTANa 2 Ca "refers to disodium calcium ethylenediamine tetraacetate.
As used herein, "GDL" refers to glucono-lactone.
In the present application, "SBMA" means [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium.
As used herein, "SiNNS" refers to N, N-dimethylaminopropyl triethoxysilane sulfonate.
In the present application, "CAPS" refers to N-cyclohexyl-3-aminopropanesulfonic acid.
The beneficial effects that this application can produce include:
1) The preparation method of the biocompatible conductive hydrogel provided by the application greatly improves the conductivity and the adhesiveness of the gel by means of the polyamphogen, and the calcium alginate is introduced to endow the gel with more excellent mechanical properties and water retention properties.
2) The biocompatible conductive hydrogel prepared by the preparation method provided by the application has the characteristics of ultra-high stretchability, transparency, self-adhesion and biocompatibility, can be well adhered to skin tissues, realizes strain/temperature dual-response sensing, has high sensitivity, can accurately monitor physiological signals such as pulse, joint bending and vocal cord vibration, and simultaneously provides an idea for preparing in-vitro/in-vivo flexible sensing devices due to the good biocompatibility of the material, and provides an economic and convenient new method for developing strain sensing equipment with high sensitivity and good mechanical adaptability.
Drawings
FIG. 1 is a schematic illustration of the preparation of sample 1# of biocompatible conductive hydrogel prepared in example 1;
FIG. 2 is a photograph of sample No. 1 adhering to human skin;
FIG. 3 is a sample 1# applied to a force sensor implementation on a human body, wherein (a) the finger is curved; (b) pulse beat; (c) real-time monitoring of vocal cord vibration;
FIG. 4 is a graph of CCK-8 cytotoxicity assay test of sample # 1;
FIG. 5 is a viable cell death staining chart of sample # 1;
FIG. 6 is a schematic illustration of the adhesion of sample No. 1 to different materials;
FIG. 7 is a schematic drawing of the stretchability of sample # 1;
FIG. 8 is a tensile strain curve test chart of sample No. 1;
FIG. 9 is a transparency test of sample No. 1; (a) is a representation of the transparency of the hydrogel under natural light; (b) To test gel clarity test patterns in the visible range using an ultraviolet spectrophotometer.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all materials used in the examples of this application were purchased commercially, and unless otherwise indicated, all conventional methods were used for testing, and all manufacturer-recommended settings were used for instrument settings. The analytical method in the examples of the present application is as follows:
and (3) testing mechanical properties by using a universal testing machine, wherein an analysis instrument is the universal testing machine, the analysis condition is that the uniaxial tension rate is 100mm/min, and the compression test rate is 0.2mm/min.
The adhesion performance is tested by a lap shear test method, the testing instrument is a universal tester, and the testing condition is that the uniaxial stretching speed is 100mm/min.
The conductivity is tested by a four-probe method, the testing instrument is a four-probe tester, and the testing condition is room temperature.
The transparency is tested by an ultraviolet spectrophotometer under the room temperature condition, in a transmission mode and in a visible light region.
Example 1
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution. FIG. 1 is a schematic diagram of the preparation, wherein a first natural polysaccharide skeleton network is formed by complexing sodium alginate with calcium ions, and then zwitterionic and hydroxy methacrylate are initiated to polymerize in situ to form a semi-interpenetrating network, so that the hydrogel based on non-covalent crosslinking completely is obtained.
The content of each substance in the prepolymer liquid is as follows:
SBMA 2.0mol/L
hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
Step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample # 1.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 4.53kPa, the breaking elongation can reach 986 percent, the stress is 2.8MPa when the compressive strain is 98 percent, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 15Pa. The conductivity of the hydrogel reaches 0.568S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 94%.
Example 2
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, and then adding a zwitterionic monomer, a hydroxyalkyl methacrylate monomer and a proper amount of initiator according to the corresponding proportion. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer is as follows
SBMA 2.0mol/L
Hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 4.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.35mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample # 2.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 1.69kPa, the breaking elongation can reach 723%, the stress is 1.2MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 8Pa. The conductivity of the hydrogel reaches 0.386S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 89%.
Example 3
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, and then adding a zwitterionic monomer, a hydroxyalkyl methacrylate monomer and a proper amount of initiator according to the corresponding proportion. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer is as follows
SBMA 2.0mol/L
Hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 2.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.25mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 3#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 1.22kPa, the breaking elongation can reach 601%, the stress is 0.96MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 7Pa. The conductivity of the hydrogel reaches 0.49S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 85%.
Example 4
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, and then adding a zwitterionic monomer, a hydroxyalkyl methacrylate monomer and a proper amount of initiator according to the corresponding proportion. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer is as follows
SBMA 2.0mol/L
Hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 1.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.15mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample # 4.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 1.01kPa, the breaking elongation can reach 554 percent, the stress is 0.83MPa when the compressive strain is 98 percent, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 6.5Pa. The conductivity of the hydrogel reaches 0.16S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 85%.
Example 5
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
SBMA 0.5mol/L
hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
1173 0.1mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample # 5.
The mechanical property test is carried out by a universal tester, and the tensile property test is carried out under the condition that the tensile rate is 100mm/min, so that the breaking stress of the material is 1.22kPa, the breaking elongation can reach 254%, and the stress when the compressive strain is 85% is 0.56MPa. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 4.3Pa. The conductivity of the hydrogel reaches 0.16S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 75%.
Example 6
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
SBMA 1.0mol/L
hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
1173 0.2mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slowly releasing to completely complex sodium alginateAnd (5) combining.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 6#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 2.43kPa, the breaking elongation can reach 546%, the stress is 1.6MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 5.2Pa. The conductivity of the hydrogel reaches 0.21S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 79%.
Example 7
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
the balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slowly releasing sodium alginateIs completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample # 7.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 8.97kPa, the breaking elongation can reach 1167%, the stress is 6.02MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 16.8Pa. The conductivity of the hydrogel reaches 0.732S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 97%.
Example 8
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, and then adding a zwitterionic monomer, a hydroxyalkyl methacrylate monomer and a proper amount of initiator according to the corresponding proportion. And (3) carrying out light-shielding treatment, and dissolving for 2-3 hours on standing and magnetic stirring to obtain a viscous and uniform mixed solution.
The content of each substance in the prepolymer is as follows
SiNNS 3.0mol/L
Hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
1173 0.5mol％
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.2mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 2-3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 3#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 2.77kPa, the breaking elongation can reach 689%, the stress is 2.3MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 8Pa. The conductivity of the hydrogel reaches 0.512S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 85%.
Example 9
Step one: firstly, dissolving sodium alginate in 10ml of deionized water to form a uniform solution, and then adding a zwitterionic monomer, a hydroxyalkyl methacrylate monomer and a proper amount of initiator according to the corresponding proportion. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer is as follows
CAPS 3.0mol/L
Hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
1173 0.5mol％
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.2mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample # 4.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 4.21kPa, the breaking elongation can reach 983 percent, the stress is found to be 4.4MPa when the compressive strain is 98 percent, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 16Pa. The conductivity of the hydrogel reaches 0.423S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 90%.
Example 10
Step one: firstly, sodium alginate is dissolved in deionized water (10 ml) to form a uniform solution, and then a zwitterionic monomer, a hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportions are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer is as follows
SBMA 3.0mol/L
Hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
Quant acure BTC 0.5mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.2mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 2-3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample # 5.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 5.18kPa, the breaking elongation can reach 1105%, the stress is 3.99MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 13.2Pa. The conductivity of the hydrogel reaches 0.503S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 94%.
Example 11
Step one: firstly, sodium alginate is dissolved in deionized water (10 ml) to form a uniform solution, and then a zwitterionic monomer, a hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportions are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer is as follows
SBMA 3.0mol/L
Hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
Quant acure BPQ 0.5mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.2mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample # 11.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 5.45kPa, the breaking elongation can reach 966%, the stress is 4.01MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 12.8Pa. The conductivity of the hydrogel reaches 0.42S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 94%.
Example 12
Step one: firstly, sodium alginate is dissolved in deionized water (10 ml) to form a uniform solution, and then a zwitterionic monomer, a hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportions are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer is as follows
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.2mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 2-3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 12#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 5.05kPa, the breaking elongation can reach 1020 percent, the stress is 3.2MPa when the compressive strain is 98 percent, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 11.2Pa. The conductivity of the hydrogel reaches 0.555S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 96%.
Example 13
Step one: firstly, dissolving carrageenan in deionized water (10 ml) at 70 ℃ to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shading treatment to obtain a mixed solution with uniform viscosity。
The content of each substance in the prepolymer liquid is as follows:
SBMA 2.0mol/L
hydroxyethyl methacrylate 1.0mol/L
Carrageenan gum 2.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the carrageenan to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 13#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 5.13kPa, the breaking elongation can reach 512%, the stress is 1.5MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 11Pa. The conductivity of the hydrogel reaches 0.216S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 89%.
Example 14
Step one: firstly, hyaluronic acid is dissolved in deionized water (10 ml) until a uniform solution is formed, EDTANa is added 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
SBMA 2.0mol/L
hydroxyethyl methacrylate 1.0mol/L
Hyaluronic acid 2.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the carrageenan to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 14#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 4.87kPa, the breaking elongation can reach 785%, the stress is 2.89MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 17Pa. The conductivity of the hydrogel reaches 0.432S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 91%.
Example 15
Step one: sodium carboxymethylcellulose is first dissolved in deionized water (10 ml) to form a homogeneous solution, and EDTANa is added 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
SBMA 2.0mol/L
hydroxyethyl methacrylate 1.0mol/L
Sodium carboxymethyl cellulose 2.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the carrageenan to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 15#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 5.13kPa, the breaking elongation can reach 698%, the stress is 3.87MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 18.3Pa. The conductivity of the hydrogel reaches 0.473S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 94%.
Example 16
Step one: firstly dissolving sodium alginate in deionized water (10 ml) to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
SBMA 2.0mol/L
hydroxypropyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 16#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 4.13kPa, the breaking elongation can reach 1208%, the stress is 2.88MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 17.3Pa. The conductivity of the hydrogel reaches 0.488S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 95%.
Example 17
Step one: firstly dissolving sodium alginate in deionized water (10 ml) to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
the balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 17#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is 3.83kPa, the breaking elongation can reach 1288%, the stress is 2.47MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 16.3Pa. The conductivity of the hydrogel reaches 0.434S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 93%.
Example 18
Step one: firstly dissolving sodium alginate in deionized water (10 ml) to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
SBMA 2.0mol/L
hydroxyethyl methacrylate 2.0mol/L
Sodium alginate 3.0wt％
1173 0.4mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 18#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 4.17kPa, the breaking elongation can reach 1018%, the stress is 3.18MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 17.6Pa. The conductivity of the hydrogel reaches 0.518S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 97%.
Example 19
Step one: firstly dissolving sodium alginate in deionized water (10 ml) to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportion are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
SBMA 2.0mol/L
hydroxyethyl methacrylate 3.0mol/L
Sodium alginate 3.0wt％
1173 0.5mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 19#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 4.66kPa, the breaking elongation can reach 1158%, the stress is 3.21MPa when the compressive strain is 98%, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 18.6Pa. The conductivity of the hydrogel reaches 0.355S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 97%.
Example 20
Step one: firstly dissolving sodium alginate in deionized water (10 ml) to form a uniform solution, adding EDTANa 2 The Fe complex is fully and uniformly mixed, and then the zwitterionic monomer, the hydroxyalkyl methacrylate monomer and a proper amount of initiator in corresponding proportions are added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
SBMA 2.0mol/L
hydroxyethyl methacrylate 1.0mol/L
Sodium alginate 3.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Fe 2+ Slow release allows the sodium alginate to be completely complexed.
Step two: injecting the monomer mixed solution into a mould, adopting photoinitiation, curing and polymerizing, and irradiating for 3 hours under ultraviolet light with the power of 8W and the wavelength of 365nm to obtain the uniform gel polymer. The biocompatible conductive hydrogel was obtained and designated sample 20#.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 3.11kPa, the breaking elongation can reach 753 percent, the stress is 2.64MPa when the compressive strain is 98 percent, and the gel is not broken. The adhesive property of the sample is tested, and the gel has good adhesive effect on rubber, glass, plastic, pigskin, wood and the like, wherein the adhesive force on the pigskin is 13.2Pa. The conductivity of the hydrogel reaches 0.332S/m through the test of a four-probe method. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 85%.
Comparative example 1
Step one: firstly dissolving sodium alginate in deionized water (10 ml) to form a uniform solution, adding EDTANa 2 The Ca complex is fully and uniformly mixed, and then a proper amount of initiator is added. Light-shielding treatment is carried out, and the mixture is dissolved for 3 hours after being placed on magnetic stirring, so as to obtain a thick and uniform mixed solution.
The content of each substance in the prepolymer liquid is as follows:
sodium alginate 3.0wt％
1173 0.3mol/L
EDTANa 2 Ca 0.5mol/L
The balance of water solvent;
step two: adding GDL into the prepolymer solution, wherein the concentration of GDL is 0.5mol/L, stirring uniformly, injecting into a mold, waiting for 4 hours to allow EDTANa 2 Ca in Ca 2+ Slow release allows the sodium alginate to be completely complexed. To obtain pure calcium alginate hydrogel.
The mechanical property test is carried out by a universal tester, the tensile property test is carried out under the condition that the tensile rate is 100mm/min, the breaking stress of the material is found to be 0.03kPa, the breaking elongation can reach 255%, the stress when the compressive strain is 45% is 0.022MPa, and the gel is not broken. And the material has no adhesion effect, and the conductivity of the hydrogel is very small by 0.015S/m through a four-probe method test. The transparency of the gel in the visible light range is detected by using an ultraviolet spectrophotometer, and the light transmittance is more than 89%.
Example 21
Taking sample No. 1 as an example, the ion conductive hydrogel is prepared into a simple flexible sensor, so that the behavior, pulse beat and vocal cord vibration of a human body are monitored, and the mechanical behavior can be well converted into an electric signal to realize the monitoring of the health of the human body. The material is found to have good application prospect in the aspect of being used as bionic ion skin.
The samples prepared in the above examples and comparative examples were subjected to performance tests, taking sample # 1 as an example.
Fig. 2 is a photograph of sample 1# adhering to human skin, and it can be seen that the material has good adhesion to human skin.
FIG. 3 is a sample 1# applied to a force sensor implementation on a human body, wherein (a) the finger is curved; (b) pulse beat; (c) real-time monitoring of vocal cord vibration; it can be seen that the gel can be used for a simple strain sensing device to well realize large-scale and small-scale motion capture of a human body.
FIG. 4 is a graph of a CCK-8 cytotoxicity test of sample No. 1, in which mouse epithelial cells are cultured by a leaching solution method, sampled for 6 hours, 24 hours, 48 hours and 72 hours, stained with a CCK-8 reagent, and subjected to test analysis by an enzyme-labeled instrument to obtain data, so that the material has excellent biocompatibility.
FIG. 5 is a chart of the viable and dead staining of sample No. 1, wherein mouse epithelial cells are selected for 2D culture, the cells are stained by using a Calcein/PI kit, and the viable and dead proliferation conditions of the cells are observed through fluorescence confocal. It can be seen that the experimental group has good cell growth condition and better biocompatibility compared with the control group.
Fig. 6 is a schematic diagram showing the adhesion of sample 1# to different materials, and it can be seen that the materials have good general adhesion.
FIG. 7 is a schematic drawing of the stretchability of sample No. 1, showing that the material has super stretchability.
FIG. 8 is a drawing showing a tensile strain curve of sample No. 1, wherein the tensile property of the material is obviously improved by comparing the drawing strain curve with pure calcium alginate gel, wherein the uniaxial tensile test is carried out by a universal tester at a test speed of 100 mm/min.
FIG. 9 is a transparency test of sample No. 1; (a) is a hydrogel transparency display under natural light; (b) To test a data graph of the transparency of a material in the visible range using an ultraviolet spectrophotometer, it can be seen that the material has high transparency.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (8)

1. A preparation method of a biocompatible conductive hydrogel with super-strong adhesion is characterized in that,
(1) Dissolving natural polysaccharide in water, adding a zwitterionic monomer, a hydroxyalkyl methacrylate monomer, an ethylenediamine tetraacetic acid metal complex and an initiator, and mixing uniformly in a dark place to obtain a prepolymer;
(2) Adding protonic acid, stirring uniformly, injecting into a mold, and releasing metal ions in the ethylenediamine tetraacetic acid metal complex to completely complex the natural polysaccharide;
(3) When photoinitiated curing polymerization is adopted, irradiating for 2-3 hours under ultraviolet light with power of 8W and wavelength of 365nm to obtain the biocompatible conductive hydrogel;
the adhesion force of the biocompatible conductive hydrogel to pigskin is 4.3-21Pa;
the transmittance of the biocompatible conductive hydrogel is 75% -97%;
the zwitterionic monomer is at least one selected from [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium, N-dimethylaminopropyl triethoxysilane sulfonate inner salt, N-cyclohexyl-3-aminopropanesulfonic acid and polyacetaine;
the hydroxyalkyl methacrylate monomer is at least one selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate;
the natural polysaccharide is sodium alginate;
the protonic acid is glucono-lactone;
the ethylenediamine tetraacetic acid metal complex is disodium calcium ethylenediamine tetraacetate;
the initiator is a water-soluble photoinitiator;
The concentration of natural polysaccharide in the prepolymer solution is 1-5wt%;
the concentration of the zwitterionic monomer is 0.5-3 mol/L;
the concentration of the hydroxyalkyl methacrylate monomer is 1-3 mol/L;
the concentration of the ethylenediamine tetraacetic acid metal complex is 0.1-0.5 mol/L;
the concentration of the initiator is 0.1-0.5 mol/L.
2. The method of claim 1, wherein the water-soluble photoinitiator is selected from at least one of 1173, quant cure BTC, quant cure BPQ.
3. The method according to claim 1, wherein the concentration of the protonic acid in the prepolymer is 0.1 to 0.5 mol/L.
4. The method according to claim 1, wherein the complexing time is 0.5 to 4 hours.
5. The method of claim 1, wherein the photoinitiation is ultraviolet light initiation.
6. The super-adhesive biocompatible conductive hydrogel prepared by the preparation method of any one of claims 1 to 5.
7. The use of the super-adhesive biocompatible conductive hydrogel of claim 6 in a multiple strain sensor.
8. Use of the super-adhesive biocompatible conductive hydrogel of claim 6 in ionic skin.
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