KR20210116889A - Biosensor - Google Patents

Abstract

The present invention relates to a biosensor. The biosensor according to the present invention comprises: a substrate; an electrode unit including a reference electrode and a working electrode formed on the substrate; and an enzyme reaction unit formed on the working electrode. The reference electrode and the working electrode contain a conductive polymer and an ionic compound. An objective of the present invention is to provide the biosensor capable of suppressing occurrence of electrode cracks due to stretching.

Description

biosensor {BIOSENSOR}

The present invention relates to a biosensor, specifically, to a biosensor comprising a conductive polymer and an ionic compound.

Biosensors are used to detect the presence of biological molecules such as proteins, amino acids, eg, DNA and/or RNA containing a specific nucleotide sequence, or other organic molecules, and typically include a glucose sensor and the like.

Such biosensors are generally performed using biological reactions such as enzymatic reactions and antigen-antibody attachment. Enzymes and antibodies not only have very high reaction specificity for selectively recognizing their reaction counterparts, but also have high reaction efficiency, so they can measure analytes with high sensitivity. It is very important to find a way to detect substances early and to be able to properly cure the symptoms at an early stage.

Various biosensors that can detect the presence of specific biomolecules include electrochemical biosensors, nano cantilever biosensors, micro or nano electromechanical systems (MEMS/NEMS), etc. In particular, in the case of electrochemical biosensors, nano cantilever biosensors Unlike sensors and MEMS/NEMS, for signal analysis of an electrochemical biosensor, it can be directly detected by an electronic device and quickly diagnosed.

Meanwhile, recently, a wearable biosensor has been attracting attention for self-diagnosis.

Korean Patent Application Laid-Open No. 2016-0140516 relates to a complex containing an electrically conductive polymer and an enzyme, and a method for regulating enzyme activity using a conductive polymer, comprising a conductive polymer matrix and an enzyme positioned inside the matrix, and the conductive polymer Disclosed is a complex for controlling the enzyme-substrate reaction, which controls the reactivity of the enzyme and the substrate by applying a voltage to the .

Korean Patent Application Laid-Open No. 2015-0097692 relates to a test apparatus for electrochemical analysis, comprising: a substrate having two or more conductive tracks disposed thereon; a reagent composition disposed on a portion of the at least one conductive track; and an upper layer covering a portion of the at least two conductive tracks to form a sample receiving chamber with the substrate, wherein at least one conductive track comprises a conductive polymer.

However, in the case of the prior art, when measuring a high-concentration substrate, the sheet resistance is rather high, so the measurement time and sensitivity are low, and there are some problems in that the electrode cracks due to stretching when attached to the body. Therefore, there is a demand for the development of a biosensor capable of increasing the degree of freedom of a user's motion and attachment position when attached to the body.

Republic of Korea Patent Publication No. 2016-0140516 (2016.12.07.) Republic of Korea Patent Publication No. 2015-0097692 (2015.08.26.)

An object of the present invention is to provide a biosensor capable of lowering the sheet resistance of a conductive polymer and suppressing the occurrence of electrode cracks due to elongation.

Another object of the present invention is to provide a biosensor capable of increasing the degree of freedom of a user's motion and attachment position when attached to the body.

In addition, an object of the present invention is to provide a biosensor having excellent measurement speed.

The present invention is a substrate; an electrode unit including a reference electrode and a working electrode formed on the substrate; and an enzyme reaction unit formed on the working electrode, wherein the reference electrode and the working electrode contain a conductive polymer and an ionic compound.

The biosensor according to the present invention has advantages in that the sheet resistance of the conductive polymer is low, and the occurrence of electrode cracks due to elongation is suppressed.

In addition, the biosensor according to the present invention has an advantage in that the user's movement is free even when the body is attached to the body due to excellent elongation.

In addition, the biosensor according to the present invention has an advantage of excellent measurement speed.

Hereinafter, the present invention will be described in more detail.

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in direct contact with another member but also a case in which another member is interposed between two members.

In the present invention, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

One aspect of the present invention is a substrate; an electrode unit including a reference electrode and a working electrode formed on the substrate; and an enzyme reaction unit formed on the working electrode, wherein the reference electrode and the working electrode contain a conductive polymer and an ionic compound.

write

The biosensor according to the present invention includes a substrate, wherein the substrate functions to provide a structural base of components constituting the biosensor.

For example, the substrate may have a hard material such as glass or be implemented in the form of a substrate film having flexible characteristics. When the substrate is implemented to be flexible, examples of specific materials that can be applied to the substrate film include polyester-based resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; Cellulose resins, such as a diacetyl cellulose and a triacetyl cellulose; polycarbonate-based resin; acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; styrenic resins such as polystyrene and acrylonitrile-styrene copolymer; polyolefin-based resins such as polyethylene, polypropylene, polyolefin having a cyclo-based or norbornene structure, and an ethylene-propylene copolymer; vinyl chloride-based resin; amide resins such as nylon and aromatic polyamide; imide-based resin; polyether sulfone-based resin; sulfone-based resins; polyether ether ketone resin; sulfide polyphenylene-based resin; vinyl alcohol-based resin; vinylidene chloride-based resin; vinyl butyral-based resin; allylate-based resin; polyoxymethylene-based resins; epoxy resin; and a film made of a thermoplastic resin such as a thermoplastic polyurethane resin (TPU), and a film made of a blend of the thermoplastic resin can also be used. In addition, a film made of a thermosetting resin or ultraviolet curable resin such as (meth)acrylic, urethane, acrylic urethane, epoxy, or silicone may be used. The thickness of the transparent optical film may be appropriately determined, but in general, it may be determined to be 1 to 500 μm in consideration of workability such as strength or handling properties, thin layer properties, and the like. In particular, 1-300 micrometers is preferable, and 5-200 micrometers is more preferable.

Preferably, the substrate is implemented in the form of a substrate film having a flexible characteristic in view of the user's degree of freedom when attaching to the body.

The base film may contain one or more suitable additives. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color inhibitors, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The base film may have a structure including various functional layers such as a hard coating layer, an anti-reflection layer, and a gas barrier layer on one or both sides of the film, and the functional layer is not limited to the above, and includes various functional layers depending on the use can do.

In addition, if necessary, the base film may be surface-treated. Examples of such surface treatment include chemical treatment such as plasma treatment, corona treatment, dry treatment such as primer treatment, and alkali treatment including saponification treatment.

electrode part

The electrode part according to the present invention is formed on a substrate and includes a reference electrode and a working electrode. Specifically, the electrode unit includes a plurality of electrodes, and these electrodes include a reference electrode and a working electrode.

In the present invention, the electrode unit serves to detect an electrical signal generated by a reaction between a substance constituting an enzyme reaction unit to be described later and a substrate included in the measurement target material, for example, glucose.

The measurement target material may be human saliva, sweat, body fluid, blood, etc., but is not limited thereto.

More specifically, the electrodes constituting the electrode part may include working electrodes and reference electrodes corresponding to the working electrodes.

In the present invention, the reference electrode and the working electrode contain a conductive polymer and an ionic compound.

In the present invention, "conductive polymer" refers to a polymer having electrical conductivity, and the conductive polymer serves to impart conductivity in the electrode part. The electrode part of the conventional biosensor is generally made of metal or carbon black, but since the reference electrode and the working electrode according to the present invention are manufactured using an electrically conductive polymer, they can be stretched in response to body movement. In addition, unlike the conventionally used conductive polymer only for a part of the wiring electrode or the working electrode, there is an advantage of simplifying the process and shortening the process time by using the entire electrode track.

In one embodiment of the present invention, the conductive polymer is one selected from the group consisting of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), polyaniline, polypyrrole, polythiophene, and polyacetylene. or more, but is not limited thereto.

However, since the conductive polymer has excellent electrical conductivity, various applications are possible, and excellent thermal and chemical stability, there is an advantage in that performance and lifespan can be improved when applied to the biosensor.

Specifically, in the present invention, the conductive polymer may be PEDOT:PSS. In this case, it is preferable because the sheet resistance is lower and the elongation is further increased when included with the ionic compound.

The ionic compound may serve to lower the sheet resistance of the biosensor and increase the elongation. Without wishing to be limited by theory, the ionic compound penetrates into the conductive polymer to increase the size of the conductive polymer, and the ionic compound acts as a plasticizer, thereby improving electrical properties and elongation properties.

In another embodiment of the present invention, the ionic compound may include at least one selected from the group consisting of a pyrrolidinium cation, an imidazolium cation, a pyridinium cation, and a lithium cation (Li ^{+ ).}

When the ionic compound includes the above-described cation, it is preferable because it has the advantage of lowering the sheet resistance of the biosensor and increasing the elongation.

In another embodiment of the present invention, the ionic compound may be represented by any one of the following Chemical Formulas 1 to 8.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 1 to 8,

R1 and R2 are each independently hydrogen or a methyl group,

n is an integer from 0 to 9 independently of each other.

When the ionic compound is Li ⁺ , a cationic compound represented by any one of Chemical Formulas 1 to 8 is preferable because the effect of lowering the sheet resistance and increasing the elongation of the biosensor is more excellent.

In another embodiment of the present invention, the ionic compound may include a sulfonylimide-based anion. When the ionic compound contains a sulfonylimide-based anion, it is preferable because it has the advantage of easy penetration into the conductive polymer.

In another embodiment of the present invention, the ionic compound may be represented by the following Chemical Formula 9 or 10.

[Formula 9]

[Formula 10]

When the ionic compound is an anionic compound represented by the formula (9) or (10), it is preferable because it has the advantage of easier penetration into the conductive polymer.

At least one ionic compound may be blended with the conductive polymer to form an electrode, however, when forming one electrode, the ionic compound may contain compounds having the same ionicity together with the conductive polymer. can be combined.

In another embodiment of the present invention, the weight ratio of the conductive polymer to the ionic compound is 1:0.1 to 1:1.5, preferably 1:0.2 to 1:1.0, more preferably 1:0.3 to 1: It may be 0.8, and in this case, it is preferable because it has advantages in improving conductivity and dispersion stability of the solution.

The reference electrode and/or the working electrode may further include a hydrogen peroxide degrading enzyme. The hydrogen peroxide decomposing enzyme may perform a role of decomposing hydrogen peroxide generated during the reaction between a substance constituting an enzyme reaction unit to be described later and a substrate included in a material to be measured, for example, glucose.

Specifically, in the case of including the hydrogen peroxide degrading enzyme, it is preferable because it is possible to measure the target material at a low voltage (0V) according to the change in the oxidation state of the hydrogen peroxide degrading enzyme, so that the accuracy of the measurement can be increased.

As the hydrogen peroxide degrading enzyme, any natural enzyme or synthetic enzyme may be used as long as it does not impair the object of the present invention. For example, Prussian blue, horseradish peroxidase (HRP, horseradish peroxidase), etc. may be used, but is not limited thereto.

The reference electrode may further include an Ag/AgCl layer, and in some cases, a pseudo-reference such as gold may be used, but is not limited thereto. In other words, the reference electrode contains a conductive polymer and an ionic compound, and may further include an Ag/AgCl layer on the layer made of the conductive polymer and the ionic compound, but is not limited thereto.

enzyme reaction part

The biosensor according to the present invention includes an enzyme reaction unit formed on the working electrode.

The enzyme reaction unit is formed on the electrode unit, and is a component that reacts with a substrate included in the measurement target material, including an enzyme that reacts with a specific substrate.

The enzyme reaction unit includes an enzyme that reacts with a substrate, and depending on the type of enzyme included in the enzyme reaction unit, a specific substance may be detected and diagnosed using a reaction with the substrate.

The enzyme is, for example, 　glucose oxidase (glucose oxidase), glucose dehydrogenase (glucose dehydrogenase), trypsin (Trypsin), aldolase (Aldolase), cholesterol oxidase (cholesterol oxidase), lactate oxidase (lactate oxidase) lock lactate dehydronase, ascorbic acid oxidase, alcohol oxidase, alcohol dehydrogenase, glutamate dehydrogenase, etc., but are not limited thereto. does not

For example, when the enzyme is a glucose oxidase, it reacts with glucose as a substrate in the measurement target material (sample or sample) by applying electrical stimulation to detect and quantify the glucose contained in the measurement target material (sample or sample). .

Specifically, the enzyme reaction unit may include a glucose oxidase or glucose dehydrogenase, and a reaction in the enzyme reaction unit and a signal sensing principle of the electrode unit will be exemplarily described as follows.

For example, when a sample, which is a material to be measured, is injected into the biosensor, glucose contained in the sample is oxidized by a glucose oxidase or glucose dehydrogenase in the enzyme reaction unit, and the glucose oxidase or glucose dehydrogenase is reduced. At this time, the electron transport mediator oxidizes the glucose oxidase or the glucose dehydrogenase, and itself is reduced. The reduced electron transport medium loses electrons on the electrode surface to which a constant voltage is applied and is electrochemically oxidized again. Since the concentration of glucose in the sample is proportional to the amount of current generated during the oxidation of the electron transport medium, the glucose concentration can be measured by measuring the amount of current.

The biosensor according to the present invention includes the above-described substrate; electrode part; and an enzyme reaction unit; In addition, it may further include other components commonly included, for example, an ion exchange membrane, a wiring unit, a wiring connection unit, a temperature sensor, and the like.

ion exchange membrane

In another embodiment of the present invention, the biosensor may further include an ion exchange membrane.

The ion exchange membrane may be further included on the enzyme reaction unit. Specifically, the ion exchange membrane is formed on the enzyme reaction unit and passes only the component to be measured from among the materials included in the sample, thereby preventing the penetration of external impurity ion components to form the enzyme reaction unit, for example. In the case of a glucose sensor, it protects glucose oxidase or glucose dehydrogenase.

In another embodiment of the present invention, the ion exchange membrane may include Nafion, but is not limited thereto. However, when the ion exchange membrane includes Nafion, it is possible to suppress the removal of the enzyme from the enzyme reaction unit, and it is preferable because it can serve as a filter to suppress measurement errors caused by substances introduced from the outside. .

temperature Senser

The temperature sensor is a component that is formed on the substrate and measures the temperature of the environment in which the substrate concentration is measured. That is, the temperature sensor transmits a current corresponding to the temperature to an IC having a current analysis function, and the IC converts the current value received from the temperature sensor according to a set conversion algorithm. Since the measured 　 substrate concentration may vary depending on the temperature, it can be used by measuring the temperature together with the 　 substrate concentration, correcting the substrate concentration according to this temperature, or matching the measured concentration and temperature. .

wiring part and wiring connections

The wiring unit includes electrodes constituting the electrode unit, specifically, reference and working electrodes, and a plurality of electrical wirings extending from the temperature sensor. The wiring unit may have the same configuration as the electrodes constituting the electrode unit, but is not limited thereto. Specifically, the wiring part may contain a conductive polymer and an ionic compound. Such a wiring unit may be connected to a sensing analysis means that performs a current analysis function through an electrical connection medium such as a flexible printed circuit board (FPCB). A pad region may be provided at an end of the wiring unit, and the FPCB may be electrically connected to the pad region by being adhered to the pad region.

The wiring connection part is a component that electrically connects the electric wires constituting the wiring part. For example, the wiring connection part may be provided in a pad region connected to the end of the wiring part, and may be configured in a form including a conductive tape or a conductive coating layer.

The principle that the sensing current saturation time is shortened by the wiring connection will be described as follows.

When a plurality of electrical wires constituting the wiring unit are electrically connected using the wiring connection unit, the reference electrode constituting the electrode unit and the working electrode are electrically shorted, so that the working electrode is compared to the reference electrode. Since it has the same effect as applying a voltage in advance, the measurement time of the sensor is shortened as the potential difference levels between these electrodes are similarly matched.

This will be described in more detail as follows.

A plurality of electrical wirings constituting the wiring unit are connected to a plurality of electrodes constituting the electrode unit, that is, a reference electrode and working electrodes, and a pad region is provided at an end of the wiring unit, that is, an end of the electrical wirings.

If, in a state in which the biosensor is not used, the plurality of electrical wirings constituting the wiring unit are not electrically connected using the wiring connection unit, the electrodes connected to the electrical wirings are in a floating state. , a slight potential deviation occurs between the respective electrodes. In this state, when measuring the substrate concentration using the biosensor, the potential deviation acts as an error component, and thus time is required to remove it.

On the other hand, in the case of the present invention, since the wiring connection part electrically connecting the electrical wirings constituting the wiring part substantially reduces the initial potential deviation between the plurality of electrodes constituting the electrode part close to zero, the substrate of the enzyme reaction part By the reaction, the saturation time of the current sensed through the electrode part is shortened to less than several seconds.

That is, in a state in which the biosensor of the present invention is not used, a plurality of electrical wirings constituting the wiring unit are electrically connected using the wiring connection unit to substantially reduce an initial potential deviation between the plurality of electrodes constituting the electrode unit. When the substrate concentration is reduced to close to zero and the user measures the substrate concentration using the biosensor, since the current is sensed by the operation of the detection and analysis means after the wiring connection is removed, the saturation time of the current sensed through the electrode part (Saturation) Time) is shortened to less than a few seconds.

In the biosensor according to the present invention, since the ionic compound is blended with the conductive polymer in the reference electrode and the working electrode, the sheet resistance of the conductive polymer is lowered and thus the electrical properties are excellent, and the elongation is increased so that the user's motion and attachment position when attached to the body There is an advantage of increasing the degree of freedom. In addition, due to the increased elongation, there is an advantage in that the occurrence of cracks in the electrode during attachment is suppressed.

The manufacturing method of the biosensor is not limited in the present invention. For example, the reference electrode and the working electrode may be prepared by screen printing or inkjet printing of a composition including the conductive polymer and the ionic compound, but is not limited thereto.

At this time, if necessary, the composition may further include a solvent, for example, alcohol-based solvents such as ethanol, isopropyl alcohol, propyl alcohol, isobutyl alcohol, normal butyl alcohol, ethylene glycol, and glycerin; ether-based solvents such as ethylene glycol monoethyl ether, butyl carbitol, and butyl carbitol acetate; ketone solvents such as acetone and methylethylcone; Ester solvents such as butyl acetate, dimethyl glutarate, and triacetin can be used.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art. In addition, "%" and "part" indicating the content hereinafter are based on weight unless otherwise specified.

Example and comparative example

Example One

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 1), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

As a substrate, a conductive polymer composition was screen-printed on TPU having a shore hardness of 95A and cured at 125°C for 30 minutes to form an electrode wiring.

After dropping the glucose oxidase on the electrode wiring used as the working electrode, it was dried at 80° C./10 minutes, and Nafion was further dropped and dried naturally for 30 minutes.

A glucose sensor was fabricated by screen-printing an Ag/AgCl composition on the upper part of the electrode wiring used as a reference electrode and curing it at 100°C for 20 minutes.

The current was measured 20 seconds after the current was stabilized by dropping 0.1 mM of glucose to the prepared glucose sensor, and it is shown in Table 1 below.

Example 2

In a state in which the sensor fabricated in the same manner as in Example 1 was stretched by 10%, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below.

Example 3

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.7 g of an ionic liquid (Formula 1), and 0.5 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

As a substrate, a conductive polymer composition was screen-printed on TPU having a shore hardness of 95A and cured at 125°C for 30 minutes to form an electrode wiring.

After dropping the glucose oxidase on the electrode wiring used as the working electrode, it was dried at 80° C./10 minutes, and Nafion was further dropped and dried naturally for 30 minutes.

A glucose sensor was fabricated by screen-printing an Ag/AgCl composition on the upper part of the electrode wiring used as a reference electrode and curing it at 100°C for 20 minutes.

In a state in which the prepared glucose sensor was stretched by 10%, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and it is shown in Table 1 below.

Example 4

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 2), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

Example 5

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 3), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

Example 6

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 4), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

Example 7

As the electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 5), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

Example 8

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 6), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

Example 9

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 7), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

Example 10

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 8), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

Example 11

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 9), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

Example 12

As an electrode wiring conductive polymer composition, 100 g of a PEDOT:PSS 1wt% mixed solution, 0.4 g of an ionic liquid (Formula 10), and 0.4 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

Using the electrode wiring conductive polymer composition, a glucose sensor was prepared in the same manner as in Example 1, and in a 10% stretched state, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below. .

comparative example One

As an electrode wiring composition, 100 g of a resin composition containing 30 wt% of Carbon Black and 3 g of phthalocyanine were mixed and stirred for 30 minutes using a stirrer.

As a substrate, an electrode wiring composition was screen-printed on TPU having a shore hardness of 95A and cured at 100° C./20 minutes to form an electrode wiring.

After dropping the glucose oxidase on the electrode wiring used as the working electrode, it was dried at 80° C./10 minutes, and Nafion was further dropped and dried naturally for 30 minutes.

A glucose sensor was fabricated by screen-printing an Ag/AgCl composition on the upper part of the electrode wiring used as a reference electrode and curing it at 100°C for 20 minutes.

The current was measured 20 seconds after the current was stabilized by dropping 0.1 mM of glucose to the prepared glucose sensor, and it is shown in Table 1 below.

comparative example 2

In a state in which the sensor prepared in the same manner as in Comparative Example 1 was stretched by 10%, 0.1 mM of glucose was dropped to measure the current 20 seconds after the current was stabilized, and are shown in Table 1 below.

ionic compounds Ionic liquid wt% in conductive polymer composition elongation
[%] Current
[nA] Example 1 Formula 1 0.4 0 48 Example 2 Formula 1 0.4 10 48 Example 3 Formula 1 0.7 10 51 Example 4 Formula 2 0.4 10 55 Example 5 Formula 3 0.4 10 50 Example 6 Formula 4 0.4 10 49 Example 7 Formula 5 0.4 10 51 Example 8 Formula 6 0.4 10 44 Example 9 Formula 7 0.4 10 49 Example 10 Formula 8 0.4 10 46 Example 11 Formula 9 0.4 10 55 Example 12 Formula 10 0.4 10 53 Comparative Example 1 - - 0 51 Comparative Example 2 - - 10 0

According to Table 1, in the case of the present example, the current is measured even when the glucose sensor is stretched by 10%, but in the case of Comparative Example 2 using a general metal electrode, it can be seen that the electrode is cut off when the glucose sensor is stretched and thus measurement is impossible. .

Claims (10)

write;
an electrode unit including a reference electrode and a working electrode formed on the substrate; and
an enzyme reaction unit formed on the working electrode;
including,
wherein the reference electrode and the working electrode contain a conductive polymer and an ionic compound;
biosensor. According to claim 1,
The ionic compound is a biosensor comprising at least one selected from the group consisting of a pyrrolidinium cation, an imidazolium cation, a pyridinium cation and a lithium cation. According to claim 1,
The ionic compound is a biosensor comprising a sulfonylimide-based anion. 3. The method of claim 2,
The ionic compound is a biosensor represented by any one of the following formulas 1 to 8:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 1 to 8,
R1 and R2 are each independently hydrogen or a methyl group,
n is an integer from 0 to 9 independently of each other. 4. The method of claim 3,
The ionic compound is a biosensor represented by the following Chemical Formula 9 or 10:
[Formula 9]

[Formula 10]

. According to claim 1,
The conductive polymer is poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid, polyaniline, polypyrrole, polythiophene, and polyacetylene, wherein the biosensor is at least one selected from the group consisting of. According to claim 1,
The weight ratio of the conductive polymer to the ionic compound is 1:0.1 to 1:1.5 of the biosensor. According to claim 1,
The enzyme reaction unit glucose oxidase (glucose oxidase), glucose dehydrogenase (glucose dehydrogenase), trypsin (Trypsin), aldolase (Aldolase), cholesterol oxidase (cholesterol oxidase), lactate oxidase (lactate oxidase) A biosensor comprising dehydrogenase (lactate dehydronase), ascorbic acid oxidase (ascorbic acid oxidase), alcohol oxidase (alcohol oxidase), alcohol dehydrogenase (alcohol dehydrogenase) or glutamate dehydrogenase. According to claim 1,
The biosensor further comprising an ion exchange membrane formed on the enzyme reaction unit. 10. The method of claim 9,
The ion exchange membrane is a biosensor comprising Nafion.