This disclosure relates to an electrode body and a method of producing an electrode body.
Measurement of electrical signals generated by a living body such as electrocardiogram, electromyogram and electroencephalogram using various devices, and control of biological functions by electrification (electrostimulation) have been used as common medical diagnosis and treatment methods. In such methods, an electrode body, which is a part of a device, serves as an interface between the device and the living body. Further, in the case of introducing a substance such as a gene by applying an electrical pulse to a tissue (cell), a device including an electrode body may also be used.
The electrode body used in the medical field generally includes conductive wiring such as metal or carbon, and a substrate material (e.g. plastic or glass) having no conductivity. The electrode body to be in direct contact with a living body is required to have biocompatibility, and devices used these days still have room for improvement in this respect.
In recent years, the merit of using a hydrogel, which is excellent in biocompatibility, in a substrate has drawn attention, and technologies of adhering an electrode material to a hydrogel is being developed.
A known example of the adhesion technology is a technology of performing electrolytic polymerization of conductive polymers with a hydrogel placed on an electrode material, and stretching the conductive polymers from the surface of the electrode material in the vicinity of the electrode material to form a conductive adhesive layer (WO 2014/157550 (PTL 1)). In addition, electrodes coated with hydrogel are known technologies (Lee et at al., Nature communications, 2014, 5, 5898 (NPL 1) and Winter et at al., Journal of Biomedical Materials Research Part B, 2006, Volume 81B, Issue 2, May 2007, Pages 551-563 (NPL 2)).
However, in the production method described in PTL 1, the polymers that play a role of adhering the porous body to the electrode are synthesized by electrolytic polymerization, so that it is necessary to provide a conductive polymer layer on the surface layer of the porous body. In addition, since the electrode and the porous body are bound together by the strong entanglement between the conductive polymers and the molecules of the porous body, there has been a demand for technologies of further firmly fixing the electrode to the porous body to make the bond more stable.
It could thus be helpful to provide an electrode body in which an electrode is firmly fixed to a gel without performing electrolytic polymerization.
The primary features of the present disclosure are as follows.
In the electrode body of the present disclosure, at a least part of a surface of an electrode is uneven, at least a part of the uneven surface of the electrode is covered with a gel, the gel has a three-dimensional network structure, and at least a part of the uneven surface is in contact with the three-dimensional network structure and is embedded inside the three-dimensional network structure.
It is preferable that the thickness of the electrode be 1 μm to 500 μm.
It is preferable that the electrode be a laminated body in which a resin layer is laminated on both surfaces of a conductive base material.
It is preferable that the conductive base material be a fabric woven from fibers and the uneven surface be a surface of the fabric. It is more preferable that the conductive base material be carbon fabric.
It is preferable that an exposed portion where the conductive base material is exposed be provided on at least a part of the surface of the electrode. It is preferable that the exposed portion be in contact with the three-dimensional network structure and be embedded inside the three-dimensional network structure.
It is preferable that the gel be a hydrogel.
It is preferable that the gel contain polyvinyl alcohol.
It is preferable that the electrode be curved at at least one location, and the curve be in contact with the three-dimensional network structure and be embedded inside the three-dimensional network structure.
It is preferable to include two or more of the electrodes.
The method of producing an electrode body of the present disclosure includes an electrode forming step of forming an electrode, an immersion step of immersing the electrode in a gel-forming solution, and a gelling step of making the gel-forming solution into a gel with the electrode immersed in the gel-forming solution.
It is preferable to repeat freezing and thawing twice or more in the gelling step.
It is preferable that at least a part of a surface of the electrode be uneven, at least a part of the uneven surface be covered with a gel, the gel have a three-dimensional network structure, and at least a part of the uneven surface be in contact with the three-dimensional network structure and be embedded inside the three-dimensional network structure.
It is preferable that the thickness of the electrode be 1 μm to 500 μm.
It is preferable that the electrode be a laminated body in which a resin layer is laminated on both surfaces of a conductive base material.
It is preferable that the conductive base material be carbon fabric.
It is preferable that an exposed portion where the conductive base material is exposed be provided on at least a part of the surface of the electrode.
It is more preferable that the gel be a hydrogel.
It is preferable that the gel contain polyvinyl alcohol.
Because the electrode body of the present disclosure has the structure described above, the electrode is firmly fixed to the gel.
In the accompanying drawings:
Hereinafter, embodiments of the electrode body and the method of producing an electrode body of the present disclosure will be described in detail with reference to the drawings.
[Electrode Body]
As illustrated in
The gel 3 has a three-dimensional network structure, and the exposed portion 24 has an uneven surface that is in contact with the three-dimensional network structure and is embedded inside the three-dimensional network structure. The resin layer 23 also is in contact with the three-dimensional network structure of the gel 3 and is embedded inside the three-dimensional network structure. Because the exposed portion 24 has an uneven surface, the three-dimensional network structure of the gel enters the irregular grooves, which firmly fixes the electrode to the gel by the anchor effect.
When the electrode has a plurality of through holes penetrating in the thickness direction, the three-dimensional network structure of the gel may enter the through holes, and the network of the three-dimensional network structure may pass through the inside of the electrode and penetrate in the thickness direction of the electrode. In this case, the electrode is fixed in the thickness direction by the three-dimensional network structure of the gel, so that the electrode can be further firmly fixed to the gel.
In the case of an electrode having a network structure on the surface and inside the electrode such as a fabric, the network structure of the conductive base material and the three-dimensional network structure of the gel are entangled with each other, and the electrode is fixed in all directions such as thickness and width. As a result, the electrode can be further firmly fixed to the gel.
The electrode 2 may have one end covered with the gel 3 and the other end not covered with the gel 3. The one end covered with the gel 3 of the electrode 2 may include, for example, the exposed portion 24 having an uneven surface. The other end of the electrode 2 that is not covered with the gel may be a lead connecting portion 27 (
In the electrode body 1 of the present embodiment, the uneven surface 21 of the electrode 2 is covered with the gel 3, and the uneven surface 21 is in contact with the three-dimensional network structure of the gel and is embedded inside the three-dimensional network structure. Therefore, the electrode 2 hardly slips off or comes off in the gel 3 and is excellent in fixability. In particular, because high molecular weight polymers starting from the surface of the electrode and extending into the gel (porous body) are tightly entangled with the molecules of the gel, the electrode and the gel are less likely to slip off during use and the fixation can be maintained for a longer period of time than in the case of adhering the gel to the electrode.
In addition, this does not require an adhesion step of polymerizing high molecular weight polymers, which facilitates the production.
Further, this does not cause deterioration of interfacial electrical properties due to the bond of high molecular weight polymers in the electrode surface.
Particularly when the uneven surface 21 is a surface of a fabric, the gel 3 (particularly the three-dimensional network structure of the gel 3) penetrates into the fabric, and the gel 3 and the fabric are intricately entwined with each other. As a result, the fabric can be further firmly fixed to the gel 3. In addition, when the electrode 2 is curved at one or more locations and the curve 28 is covered with the gel 3 (see
The above example describes the case where the exposed portion 24 is uneven. However, the resin layer 23 may be an uneven portion, or the resin layer 23 may be fibers or other materials that can be easily penetrated by the gel.
(Electrode)
Examples of the electrode include a conductive base material such as a carbon electrode, a metal electrode, a stretchable electrode, and a composite electrode thereof. Examples of the composite electrode include a combination of a metal electrode and a carbon electrode, a combination of a metal electrode and a stretchable electrode, and a combination of a carbon electrode and a stretchable electrode. For example, it is possible to use a composite electrode where carbon particles, which are carbon electrodes, are embedded in the surface of a stretchable electrode. Among these, a carbon electrode is preferable from the viewpoint of flexibility and long-term stability of the resistance value of the electrode.
The electrode 2 may be a body of single layer of the conductive base material 22 described above or may be a laminated body including, for example, the conductive base material 22 and a resin layer 23 such as an insulating resin layer. For example, it may be a laminated body where the resin layer 23 is laminated on both surfaces of the conductive base material 22 (
The electrode 2, as a connection structure that connects to an external power source or the like, may include wiring 25 and a connecting portion 26 for electrically connecting the wiring 25 to the conductive base material 22 (
Specific examples thereof include an electrode 2 that is a laminated body where a resin layer 23 (e.g. an insulating resin layer such as PDMS) is provided on both surfaces of a conductive base material 22 (e.g. carbon fabric), an exposed portion 24 where one surface of the conductive base material 22 is exposed is provided near one end, and a lead connecting portion 27 where both surfaces are exposed is provided near the other end, as illustrated in
—Carbon Electrode—
The carbon electrode is not particularly limited as long as it can be used as an electrode. Specific examples thereof include a graphene sheet, an aggregate of carbon nanotubes, an aggregate of carbon particles, and a carbon cloth such as carbon fabric. Examples of the carbon fabric include a fabric woven from fibers impregnated with carbon nanotubes. Among these, carbon fabric is preferable from the viewpoint of being excellent in flexibility and long-term stability of the resistance value of the electrode.
It is also acceptable to use a fabric impregnated with a conductive material such as conductive polymers or metal particles, yet carbon fabric is preferable from the viewpoint of biocompatibility.
—Metal Electrode—
The metal electrode is not particularly limited as long as it can be used as an electrode. Specific examples thereof include gold, platinum, titanium, aluminum, and tungsten. Among these, gold or platinum is preferable from the viewpoint of stability and excellent biosafety.
—Stretchable Electrode—
The stretchable electrode is not particularly limited as long as it is an elastomer that can be used as an electrode. That is, it is possible to use an elastomer having ionic conductivity or conductivity. Specific examples include polyurethane, silicone rubber, and fluororubber, among which polyurethane is preferred.
—Resin Layer—
The resin layer 23 may be laminated so as to be in contact with the conductive base material 22, or may be laminated via another layer. Among these, it is preferable that the resin layer 23 be in contact with the conductive base material 22 from the viewpoint of weight reduction.
Examples of the material forming the resin layer 23 include polydimethylsiloxane, polyurethane, polypropylene, polylactic acid, poly(lactide-co-glycolide) copolymer, polydioxanone, acrylonitrile butadiene styrene copolymer, acrylic ester, acrylonitrile ethylene propylene rubber styrene copolymer, acrylonitrile styrene copolymer, acrylonitrile styrene acrylate, polybutadiene, bismaleimide triazine, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyclic butyl terephthalate, cresol formaldehyde, carboxymethyl cellulose, nitrocellulose, hydrin rubber, cellulose propionate, chlorinated vinyl chloride, chloroprene rubber, casein, cellulose triacetate, diallyl phthalate, ethylene chlorotrifluoroethylene copolymer, ethylenediaminetetraacetic acid, ethylene ethyl acrylate, ethylene methyl acrylate, ethylene methacrylic acid, epoxy resin, ethylene propylene diene terpolymer, ethylene tetrafluoroethylene copolymer, ethylene vinyl acetate copolymer, ethyl vinyl ether, perfluoro rubber, polyethylene, polystyrene, butyl rubber, isoprene rubber, diphenylmethane isocyanate, melamine formaldehyde, nitrile rubber, polymethyl methacrylate, polyimide, polyethylene terephthalate, polycarbonate, polyetheretherketone, polyisobutylene, polymethylmethacrylate, polyvinyl acetate, polyvinyl chloride, nylon, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl pyrrolidone, styrene butadiene, silicone, polyester, Teflon® (Teflon is a registered trademark in Japan, other countries, or both), and polytetrafluoroethylene. Among these, an insulating resin is preferable, and polydimethylsiloxane (PDMS) is more preferable from the viewpoint of fixability to the conductive base material.
By providing a resin layer as describe above, it is easy to maintain the curved structure of the conductive base material even in the case of using a conductive base material with high flexibility.
—Exposed Portion—
The exposed portion 24 may be provided at one location or at a plurality of locations on the surface of the electrode. It is preferable that at least a part of the exposed portion 24 be provided with the uneven surface, and it is more preferable that the whole exposed portion 24 be provided with the uneven surface.
The exposed portion 24 may be provided on both surfaces of the electrode, or may be provided on one surface. Among the above, the exposed portion 24 is preferably provided on one surface from the viewpoint of being able to supply electricity partially. In the case where a conductive base material not covered with a resin layer is used as the electrode, the entire surface of the electrode is the exposed portion.
—Wiring—
Common wiring can be used as the wiring 25.
—Connecting Portion—
The connecting portion 26 is preferably made of the same material as the material forming the conductive base material from the viewpoint of conductive efficiency. For example, when carbon fabric is used as the conductive base material 22, the connecting portion 26 is preferably formed by drying a dispersion of carbon nanotubes.
—Lead Connecting Portion—
Examples of the lead connecting portion 27 include one end of the conductive base material 22 not covered with the gel 3 (e.g. the end opposite to the exposed portion) (
—Curve—
The electrode 2 preferably has at least one curve 28 from the viewpoint of further firmly fixing the electrode to the gel.
The curve 28 may be in a curved shape (
In the electrode 2, the number of the curve 28 is preferably at least one and may be more than one. When there is a plurality of curves 28, each curve may be provided continuously or may be provided at intervals.
The radius of curvature of the curve 28 is preferably more than 0 mm from the viewpoint of the fixability between the electrode and the gel. For example, when an exposed portion 24 is provided, the center of curvature of the curve may be on the exposed portion 24 side.
When a plurality of curves 28 are provided, the centers of curvature of the respective curves may be on the same side or on different sides. Further, the radii of curvature of the respective curves may be the same or different.
The radius of curvature of the curve may be a radius of curvature at any one point within the curve in a cross section in the thickness direction of the electrode. As used herein, the cross section in the thickness direction of the electrode is a cross section cut in the laminating direction of the conductive base material and the resin layer, which is a cross section including the curve.
The thickness of the electrode 2 is preferably 1 μm to 500 μm and more preferably 1 μm to 300 μm from the viewpoint of flexibility of the electrode body.
The shape of the electrode 2 in a plan view before being curved is not particularly limited. For example, it may be in a substantially polygonal shape such as a rectangle, a substantially circular shape, or a ladle shape (
The shape of the electrode 2 after being curved is not particularly limited. For example, it may have a shape where a curve is provided on any substantially straight line on the electrode surface. In addition, the exposed portion may be deformed so as to conform to the shape of an animal, an organ, etc. to which it is applied.
At least a part of the surface of the electrode 2 is uneven.
Examples of the unevenness include saw-toothed unevenness in a cross section in the thickness direction of the electrode, unevenness having a plurality of through holes penetrating in the thickness direction of the electrode, and surface unevenness formed by a fabric woven from fibers. Among these, unevenness having a plurality of through holes and surface unevenness formed by a fabric is preferable from the viewpoint of further firmly fixing the electrode to the gel, and surface unevenness formed by a fabric is more preferable from the viewpoint of excellent followability to the gel and excellent flexibility.
Examples of the fabric forming the surface unevenness include a carbon cloth such as the carbon fabric described above, and a fabric impregnated with a conductive material. Carbon fabric is preferable from the viewpoint of biocompatibility.
The uneven surface 21 may be provided on any part of the electrode 2, yet it is preferably provided on the exposed portion 24 from the viewpoint of preventing a measurement site from slipping off.
(Gel)
The gel 3 is preferably one having excellent flexibility and biocompatibility and is more preferably a hydrogel. The gel 3 is preferably an ionic conductor. The gel preferably has a three-dimensional network structure. Examples of the three-dimensional network structure (gel network) include a structure having linear portions and coupling portions that couple the linear portions.
Hydrogel is a gel in which water is retained as a solvent in a three-dimensional network structure, which exhibits extremely excellent water absorption. Gels, whether natural or synthetic, are often hydrogels that contain water. Most of the soft tissues that make up a living body, such as cornea, crystalline lens, vitreous body, muscles, blood vessels, axons, and cartilage, are typical hydrogels containing 60% to 80% water in the network structure of biopolymers. Further, although hard tissues such as bones and teeth are not hydrogels themselves, they often have a structure in which a gel-like substance such as collagen is filled in gaps of inorganic hydroxyapatite. Therefore, there are many hydrogels that are derived from a living body and are excellent in biocompatibility.
Specific examples of the hydrogel include agarose gel, collagen gel, glucomannan gel, polyacrylamide gel, polyacrylamide-2-methylpropanesulfonic acid gel, fibrin gel, polyvinyl alcohol gel, polyhydroxyethyl methacrylate gel, silicone hydrogel, polyvinylpyrrolidone gel, polyethylene glycol gel, poly-2-acrylamide-2-methylpropanesulfonic acid gel, alginic acid gel, carrageenan gel, chitosan gel, poly-N-isopropylacrylamide gel, acrylic acid gel, polystyrene sulfonate gel, and a mixture of two or more of these (composite gel). Among these, a hydrogel containing polyvinyl alcohol is preferable, and a hydrogel consisting only of polyvinyl alcohol is more preferable, from the viewpoint of having high safety to living bodies and having no biodegradability.
The gel can include materials other than the material forming the gel as long as the effects of the present disclosure can be obtained. Specific examples include cells, proteins (antibodies, antigens, enzymes, cell growth factors, etc.), nucleic acids such as DNA and RNA, peptide molecules, microparticles and nanoparticles, fluorescent and phosphorescent molecules, and redox agents.
The water content of the gel is not particularly limited. However, it is preferably 60 mass % to 99.5 mass %, more preferably 70 mass % to 99 mass %, and further preferably 80 mass % to 99 mass %.
In the electrode body of the present embodiment, the gel may cover the entire electrode (for example, the entire electrode except the connection structure such as the wiring 25 and the lead connecting portion 27) (
In the electrode body of the present embodiment, the gel covers at least a part of the uneven surface 21 of the electrode. The gel may cover all over the uneven surface 21 or may cover a part of the uneven surface 21. In the case where there is a plurality of uneven surfaces 21, it is preferable that the gel cover at least one uneven surface 21, and the gel may cover all the uneven surfaces 21.
Further, it is preferable that the gel cover the exposed portion 24 and/or the curve 28 of the electrode. In the case where there is a plurality of exposed portions 24 and/or curves 28, it is preferable that the gel cover at least one exposed portion 24 and/or curve 28, and the gel may cover all the exposed portions 24 and/or curves 28.
The electrode 2 may be covered with the gel 3 by being in contact with the gel 3 or may be covered with the gel 3 via another layer. Among these, it is preferable that the electrode 2 be in contact with the gel 3 from the viewpoint of further firm fixing.
Note that the “cover” means that the entire surface of the target region of the electrode 2 is covered with the gel 3.
The “cover” preferably means that the entire surface of the target region is in contact with the three-dimensional network structure of the gel and is embedded inside the three-dimensional network structure.
For the electrode body 1 of the present embodiment, the number of the electrode 2 may be one or two or more (for example, 2 to 64). For example, in the case where the device is used for electrical stimulation of muscles, the number of the electrode may be two, and in the case where the device is used not only for electrical stimulation but also for sensing brain waves, the number may be 2 to 64 from the viewpoint of obtaining more detailed information.
For the electrode body of the present embodiment, the combination of the electrode 2 and the gel 3 is preferably, for example, a combination of an electrode that is a laminated body of carbon fabric and PDMS, and a hydrogel that contains polyvinyl alcohol, from the viewpoint of long-term stability of the resistance value of the electrode, difficulty in peeling off the gel from the electrode, and safety in vivo.
The electrode body of the present embodiment can be used as a gel electrode that is embedded in a living body by, for example, being attached to an organ of a living body, or being embedded under the skin. Specifically, it can be used as a measurement stimulating electrode to be attached to an organ, an electrode for stimulating a throat muscle, an electrode to be attached to the brain surface, or an electrode to be inserted into a gap in the brain, for example.
The electrode body of the present embodiment may be embedded so that the portions covered with the gel are embedded inside a body and the portions not covered with the gel are exposed outside the body.
[Method of Producing Electrode Body]
The method of producing an electrode body of the present embodiment may be a method including, for example, an electrode forming step of forming an electrode, an immersion step of immersing the electrode in a gel-forming solution, and a gelling step of making the gel-forming solution into a gel with the electrode immersed in the gel-forming solution.
(Electrode Forming Step)
In the electrode forming step, a resin layer 23 is formed on a substrate 29 for forming electrode (
In the electrode forming step, a resin layer 23 is formed on a substrate 29 for forming electrode (
Examples of the substrate 29 for forming electrode include a plate made of glass, plastic, cloth, wood, or the like. Among these, a glass plate is preferable because it is flat and has low adhesion to the electrode.
Examples of the method of applying the material forming the resin layer onto the substrate 29 for forming electrode include spin coating and spray coating.
The conditions of the application can be appropriately determined depending on the viscosity of the material to be applied, the thickness of the layer to be formed, and the like. For example, the conditions for spin coating PDMS on a slide glass may be a rotation rate of 1000 rpm to 2000 rpm and a time of 20 seconds to 60 seconds.
The method of curing the material forming the resin layer can be appropriately determined depending on the material used. For example, a method of placing the substrate for forming electrode on a hot plate having a temperature of 120° C. or higher and heating the substrate may be used.
Examples of the method of applying the material forming the resin layer onto the resin layer include spin coating and spray coating. For example, a method of applying PDMS on a PDMS layer with a rotation rate of 500 rpm to 600 rpm and a time of 20 seconds to 30 seconds may be used. The rotation rate is preferably lower than that when forming the resin layer on the substrate for forming electrode, from the viewpoint of uniformly applying the resin without gap, obtaining a resin layer having an appropriate thickness, and further firmly adhering the resin layer to the electrode.
Examples of the method of providing the connecting portion 26 include a method of placing the wiring 25 on the conductive base material 22, dropping a few drops of carbon nanotube dispersion or the like, and drying it.
Examples of the method of providing the exposed portion 24 include a method of covering portions other than a region to be exposed on the conductive base material 22 with the material forming the resin layer, and, for example, heating it to cure the material.
(Immersion Step)
An electrode body mold 4 having a through hole in the center is placed on a substrate 5 for forming electrode body (
An electrode body mold 4 having a through hole in the center is placed on a substrate 5 for forming electrode body (
Examples of the electrode body mold 4 include a mold made of silicone rubber, PDMS, or the like.
The shape of the mold is not particularly limited as long as an electrode body having a desired shape can be formed. The number of the used mold may be one, or a combination of a plurality of molds may be used. Examples of the case of two molds include two rectangular molds having a rectangular through hole in the center in a plan view (
Examples of the gel-forming solution 31 include a solution containing components constituting the gel describe above. The solution may be, for example, an aqueous solution, or an organic solvent solution (e.g. a mixed solution of DMSO and water).
By using a highly viscous solution as the gel-forming solution 31, the gel-forming solution easily penetrates into the holes in the electrodes. Particularly in the case where the conductive base material is a fabric woven from fibers, it is preferable that the gel permeate the conductive base material from the viewpoint of further firmly fixing the electrode to the gel and preventing coming off.
(Gelling Step)
Examples of the method of making the gel-forming solution into a gel with the electrode immersed in the gel-forming solution include a method of repeatedly freezing and thawing, a method of evaporating the solvent of the gel-forming solution, and a method of irradiating the solution with ultraviolet rays.
In the case of the method of repeatedly freezing and thawing, it is preferable to repeat the freezing and thawing at least twice from the viewpoint of further firmly fixing the electrode to the gel and improving the strength of the gel as a substrate.
The freezing may be performed under conditions of a temperature of −30° C. to −15° C. and a time of 120 minutes to 180 minutes, for example.
The thawing may be performed under conditions of a temperature of 0° C. to 25° C. and a time of 20 minutes to 60 minutes.
(Sterilization)
The electrode body of the present embodiment may be used after being sterilized.
The sterilization method is not particularly limited, and examples thereof include high-temperature and high-pressure saturated steam sterilization (autoclave sterilization), gas sterilization, boiling water sterilization, sterilization with a drug (e.g. alcohol, or hypochlorous acid). These sterilization methods can be appropriately used depending on the use of the electrode body.
The following describes the present disclosure in more detail based on Examples. However, the present disclosure is not limited to these Examples.
The following materials were used in Examples.
Electrodes A were prepared with the following method.
The sheet resistance of the conductive base material was 5.2 S)/sq. The sheet resistance is a value measured by the two-terminal method using DL-92 manufactured by KENWOOD.
Subsequently, the electrode A was embedded in a gel.
The dimensions of the obtained electrode body are indicated in
An electrode body was obtained in the same manner as in Example 1 except that a conductive base material having a thickness of 120 μm in which gold was deposited on the surface of a plastic film (product name: Saran Wrap, manufactured by Asahi Kasei Corp.) was used as the conductive base material. The sheet resistance of the conductive base material used was 3.7 S)/sq.
Electrodes B were prepared with the following method.
Subsequently, the prepared electrodes were embedded in a gel.
The sheet resistance of the carbon fabric used was 5.2 S)/sq.
The resistance from the tip of the wiring of the prepared electrode to the center of the exposed portion of the carbon fabric (see
The electrode body prepared in Example 1 was embedded behind the neck of a rat.
(Evaluation)
A carbon fabric similar to that of Example 1 was cut into a size of a length of 10 mm, a width of 50 mm, and a thickness of 300 μm, and covered with a 20 wt % PVA solution (a mixture where a volume ratio of solvent:DMSO to water was 4:1) to obtain a sample (CF 300 μm) having a length of 30 mm, a width of 30 mm, and a thickness of 1000 μm. The conditions of gelling of PVA were the same as in Example 2.
A sample (CF 600 μm) was obtained in the same manner as the sample (CF 300 μm) except that two carbon fabrics were stacked. A sample (CF 900 μm) was obtained in the same manner as the sample (CF 300 μm) except that three carbon fabrics were stacked. The flexibility was evaluated using the sample (CF 600 μm) and the sample (CF 900 μm).
The three types of samples were placed on a thin glass rod and left at a temperature of 25° C. for one minute.
The results are illustrated in
(Electric Double Layer Capacity)
The electrode bodies prepared in Example 1 and Comparative Example 1 were subjected to cyclic voltammetry measurement and impedance measurement using an electrochemical measurement system (product number: Model 760C, manufactured by CH Instruments, Inc.). An Ag/AgCl electrode was used as a reference electrode, and the electrode at the exposed portion was used as a working electrode.
In the cyclic voltammetry measurement, the sweep potential was 0 V to 0.5 V, and the sweep rate was 0.05 mV/s.
In the impedance measurement, the two-terminal method was used to apply an AC voltage having a frequency of 1 Hz to 100000 Hz and an amplitude of 0.05 V to the electrodes to perform the measurement.
The electric double layer capacity was 1.7×10−4 F/cm2 for gold and 8.5×10−4 F/cm2 for carbon fabric (
In addition, the impedance of Example 1 was lower than that of Comparative Example 1 (
(Combination of Gel and Electrode)
A carbon fabric similar to that of Example 1 was cut into a size of a length of 10 mm, a width of 10 mm, and a thickness of 300 μm, and covered with a 20 wt % PVA solution (a mixture where a volume ratio of solvent:DMSO to water was 4:1) to obtain a sample (CF) having a length of 30 mm, a width of 30 mm, and a thickness of 1000 μm. The conditions of gelling of PVA were the same as in Example 2.
An electrode in which gold was deposited on the surface of a plastic film with a smooth surface (product name: Saran Wrap, manufactured by Asahi Kasei Corp.) was covered with a 20 wt % PVA solution (a mixture where a volume ratio of solvent:DMSO to water was 4:1) to obtain a sample (plastic film) having a length of 10 mm, a width of 10 mm, and a thickness of 120 μm. The conditions of gelling of PVA were the same as in Example 2.
The samples were being pulled in the width direction (the cross direction in
(Mechanical Strength)
A carbon fabric similar to that of Example 1 was cut into a size of a length of 5 cm, a width of 1 cm, and a thickness of 300 μm, and a portion of 1 cm from one end in the length direction was covered with a 20 wt % PVA solution (a mixture where a volume ratio of solvent:DMSO to water was 4:1) to obtain a test piece (CF) (
A conductive base material in which gold was deposited on a plastic film similar to that of Comparative Example 1 was cut into a size of a length of 5 cm, a width of 1 cm, and a thickness of 120 μm, and a portion of 1 cm from one end in the length direction was covered with a 20 wt % PVA solution (a mixture where a volume ratio of solvent:DMSO to water was 4:1) to obtain a test piece (plastic gold-deposited film) (
The other end of the test piece, which was not covered with the PVA gel, was pulled upward in
The results are illustrated in
As the force gradually increased, the carbon fabric of the test piece (CF) (carbon fabric) gradually expanded, and the carbon fabric was torn when the force reached 4.9 N. During the test, the carbon fabric and the PVA gel were firmly fixed together.
On the other hand, for the test piece (plastic gold-deposited film) (Au+plastic film), the plastic gold-deposited film came off from the PVA gel when the force reached 0.1 N.
Electrodes C were prepared with the following method.
Subsequently, the prepared electrode was embedded in a gel.
The shape and dimensions of the obtained hydrogel organic electrode are illustrated in
All the animal experiments were conducted with the approval of Animal Health Committee of Tohoku University Graduate School of Medicine.
An adult rat was continuously anesthetized during the period of craniotomy and neurography. The head of the anesthetized rat was fixed to a fixing device, and a cortical region of 12 mm×12 mm of both hemispheres were exposed by craniotomy. The rat and the fixing device were placed inside a Faraday cage with a metal wire base to reduce noise.
A conventional subdural electrode (manufactured by Unique Medical, a conventional product that was an intracranial electrode and an electrode in which a flat metal was covered with a resin, and that did not meet the requirements of claim 1 of the present application) and the prepared hydrogel organic electrode (electrode body) were placed on the exposed cortex of the rat and fixed with tweezers (
The potential waveform was successfully measured with the conventional subdural electrode and the hydrogel organic electrode (
In the electrode body of the present disclosure, the electrode is firmly fixed to the gel. Therefore, the electrode body of the present disclosure can be used as a gel electrode or the like to be embedded in a living body.
Number | Date | Country | Kind |
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2017-247039 | Dec 2017 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2018/047667 | 12/25/2018 | WO | 00 |