KR20200062944A - Glucose Sensor - Google Patents

Abstract

The present invention includes: a substrate; an electrode unit formed on the substrate; an electrode protection and electron transport unit formed to cover the electrode unit on the electrode unit; and a glucose reaction unit formed on the electrode protection and electron transport unit. The glucose reaction unit provides a glucose sensor including an enzyme and an immobilizing agent. The present invention can shorten the current saturation time.

Description

Glucose Sensor

The present invention relates to a glucose sensor, and more particularly, to prevent the loss of enzymes, excellent durability, and to a glucose sensor capable of shortening the saturation time of the current.

Recently, due to the rapid increase in patients with diabetes and metabolic diseases, quantitative analysis of glucose in blood becomes important, and research on a glucose sensor that measures the concentration of glucose electrochemically has been actively conducted.

Most studies of glucose sensors are based on enzymes such as glucose oxidase or glucose dehydrogenase, which promotes the oxidation of glucose to gluconolactone [Registration No. 10-1107506, Korea] Reference].

The glucose sensor is based on the principle of measuring the concentration of glucose in the analyte by measuring the current generated by transferring electrons generated by the oxidation of glucose in the analyte by an enzyme to the electrode.

However, as the enzyme is lost in the process of repeating the measurement using the glucose sensor, the durability of the glucose sensor is deteriorated.

Meanwhile, the glucose sensor may be divided into an invasive type measuring glucose contained in blood, and a non-invasive type measuring glucose contained mainly in saliva and sweat.

In the case of the conventional non-invasive glucose sensor using human body saliva and sweat as a sample, since the glucose contained in the sample is very small, there is a problem that a sensing current saturation time enabling meaningful measurement takes a long time.

Therefore, there is a need to develop a technology for a glucose sensor that is excellent in durability by preventing loss of enzyme and can shorten a saturation time of a current.

Republic of Korea Registered Patent No. 10-1107506

One object of the present invention is to provide a glucose sensor that is excellent in durability by preventing loss of enzyme and can shorten a saturation time of an electric current.

On the one hand, the present invention is a substrate; An electrode portion formed on the substrate; An electrode protection and electron transport unit formed to cover the electrode unit on the electrode unit; And a glucose reaction unit formed on the electrode protection and electron transport unit, and the glucose reaction unit provides a glucose sensor including an enzyme and an immobilizing agent.

The glucose sensor according to an embodiment of the present invention may further include an ion exchange membrane formed on the glucose reaction unit.

In one embodiment of the present invention, the electrode protection and electron transport unit may include an electrode protection material, an electron transporter and a binder.

In one embodiment of the present invention, the electrode protection material may include carbon.

In one embodiment of the present invention, the electron transporter may include Prussian blue.

In one embodiment of the present invention, the immobilizing agent is at least one selected from the group consisting of a polymer compound having an amine group, a hydroxyl group or a sulfonic acid group, a compound having an aldehyde group, a compound having a carboxy group, a compound having an unhydride group, and an epoxy compound It may include.

In one embodiment of the present invention, the polymer compound having the amine group, hydroxy group or sulfonic acid group is at least one selected from the group consisting of chitosan, perfluorosulfonic acid resin, polypyrrole, polydopamine, polyethyleneimine and polyaniline. It may include.

In one embodiment of the present invention, the compound having an aldehyde group is glutaric aldehyde, terephthalaldehyde, anthracene-9,10-dicarboxyaldehyde, 4,4'-biphenyldicarboxyaldehyde, 1,2-benzenedicarboxy Aldehyde, 1,3-diformylbenzene, 1,4-butanedial and naphthalene dialdehyde.

In one embodiment of the present invention, the compound having the carboxyl group is propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonandaioic acid, decandioic acid, undecanedioic acid Iksan and dodecanedioic acid may include one or more selected from the group consisting of.

In one embodiment of the present invention, the compound having an anhydride group may include one or more selected from the group consisting of acetic anhydride and butanediic anhydride.

In one embodiment of the present invention, the epoxy compound is 1,5-hexadiene diepoxide, bisphenol A diglycidyl ether, diepoxybutane, 2,2'-dimethyl-2,2'-bioxy Lan and dicyclopentadiene diepoxide.

In one embodiment of the present invention, the immobilizing agent may be capable of π-conjugation.

In one embodiment of the present invention, the immobilizing agent may be a compound having an aldehyde group capable of π-conjugation.

In one embodiment of the present invention, the immobilizing agent may include a polymer compound having an amine group, a hydroxyl group, or a sulfonic acid group, and a compound having an aldehyde group capable of π-conjugation.

In one embodiment of the present invention, the enzyme may include glucose oxidase or glucose dehydrogenase.

The glucose sensor according to the present invention is excellent in durability by preventing the loss of enzymes.

In addition, the glucose sensor according to the present invention may shorten the measurement speed for glucose concentration. In particular, according to the present invention, by reducing the saturation time (Saturation Time) of the current sensed through the electrode of the non-invasive glucose sensor, it is possible to provide a glucose sensor with a very fast measurement rate for glucose concentration.

In addition, the glucose sensor according to the present invention can be thinned by configuring a layer to perform electrode protection and electron transport functions as a single layer.

1 is a schematic cross-sectional view of a glucose sensor according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

1 is a schematic cross-sectional view of a glucose sensor according to an embodiment of the present invention.

Referring to FIG. 1, a glucose sensor according to an embodiment of the present invention includes a substrate 10, an electrode portion 20, a conductive oxide film 30, an electrode protection and electron transport portion 40, a glucose reaction portion 50, and It includes an ion exchange membrane (60).

The substrate 10 functions to provide a structural base of components constituting the glucose sensor.

For example, the substrate 10 may be implemented in the form of a base film having a rigid material such as glass or flexible characteristics.

Examples of specific materials that can be applied to the base film when the substrate 10 is flexibly implemented include polyester-based resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; Cellulose-based resins such as diacetyl cellulose and triacetyl cellulose; Polycarbonate-based resins; Acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based resins such as polyethylene, polypropylene, polyolefins having a cyclo-based or norbornene structure, and ethylene-propylene copolymers; Vinyl chloride resin; Amide resins such as nylon and aromatic polyamides; Imide resin; Polyethersulfone-based resins; Sulfone resins; Polyether ether ketone-based resins; Polyphenylene sulfide resins; Vinyl alcohol-based resins; Vinylidene chloride-based resins; Vinyl butyral resins; Allylate-based resins; And thermoplastic resins such as polyoxymethylene resins, and blends of the thermoplastic resins can also be used. In addition, thermosetting resins such as (meth)acrylic, urethane-based, acrylic urethane-based, epoxy-based, and silicone-based resins or ultraviolet curable resins can also be used.

The base film may contain one or more suitable additives. Examples of the additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, coloring inhibitors, flame retardants, nucleating agents, antistatic agents, pigments, coloring agents and the like. The base film may be 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 according to the use can do.

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

The thickness of the substrate 10 may be appropriately determined, but generally, it may be determined to be 1 to 500 μm in consideration of workability such as strength and handling properties, thin layer properties, and the like. In particular, 1 to 300 µm is preferable, and 5 to 200 µm is more preferable.

The electrode portion 20 is composed of a plurality of electrode portions formed on the substrate 10. The electrode unit 20 senses an electrical signal generated by the reaction of the substances constituting the glucose reaction unit 50 to be described later and the glucose contained in the measurement target material. For example, the material to be measured may be saliva, sweat, body fluid, blood, etc. of the human body, but is not limited thereto.

For example, the electrode part 20 may include a plurality of working electrode parts and a plurality of reference electrode parts corresponding to the working electrode parts.

The electrode portion 20 is gold (Au), silver (Ag), copper (Cu), aluminum (Al), platinum (Pt), palladium (Pd), chromium (Cr), titanium (Ti), tungsten (W) , Niobium (Nb), Tantalum (Ta), Vanadium (V), Iron (Fe), Manganese (Mn), Nickel (Ni), Zinc (Zn), Tin (Sn), Molybdenum (Mo), Cobalt (Co) Or alloys thereof (eg, silver-palladium-copper (APC)). These may be used alone or in combination of two or more.

The electrode portion 20 may be bonded on the substrate 10 by an adhesive layer.

The adhesive layer may be composed of an adhesive used in the art, for example, an ultraviolet curing adhesive. Examples of the UV curable adhesive include (meth)acrylate-based adhesives, N/thiol-based adhesives, unsaturated polyester-based adhesives, and other adhesives using photo-radical polymerization or epoxy-based adhesives, oxetane-based adhesives, epoxy/oxetane-based adhesives, and vinyl. And an adhesive using a photo cationic polymerization reaction such as an ether-based adhesive.

The thickness of the adhesive layer may be 0.5 to 5 μm, preferably 1.5 to 2 μm. Sufficient adhesion may be exhibited in the thickness range.

A conductive oxide film 30 may be additionally formed in the upper and/or lower regions of the electrode portion 20. The conductive oxide film 30 may prevent oxidation of the electrode portion 20 to improve the reliability of the electrical signal sensed by the electrode portion 20.

For example, the conductive oxide film 30 may include Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), or the like.

The electrode protection and electron transport unit 40 is formed to cover the electrode unit on the electrode unit 20 to protect the electrodes constituting the electrode unit 20, and at the same time, the electrical sensitivity of the electrode unit 20 through electron transport. It performs the function of raising. When the glucose sensor further includes a conductive oxide film 30 in the upper region of the electrode part 20, the electrode protection and electron transport part 40 is on the conductive oxide film 30 and the conductive oxide film 30 and the electrode part ( 20) is formed to cover the resulting electrode portion 20 is protected.

The electrode protection and electron transport unit includes an electrode protection material, an electron transporter, and a binder.

The electrode protection and electron transport unit may be formed by printing and drying a paste containing an electrode protection material, an electron transporter, and a binder on the electrode unit 20.

The binder serves as a matrix for supporting the electrode protective material and the electron transporter to form an electrode protection and electron transport unit.

As the binder, one commonly used in the art may be used. For example, a polyester resin, a polyethylene resin, or the like can be used as the binder.

The content of the binder may be 5 to 50% by weight with respect to 100% by weight of the total solids of the paste forming the electrode protection and electron transport portion. If the content of the binder is less than 5% by weight, the electrode protection function may be deteriorated, and if it is more than 50% by weight, the viscosity of the paste may increase, making it difficult to protect the electrode and form an electron transport unit.

The electron transporter is a component that performs the function of electron transport, oxidizes glucose oxidase or glucose dehydrogenase, and after being reduced, loses electrons at the electrode surface to which a certain voltage is applied and oxidizes again electrochemically.

For example, the electrode protection and electron transport unit 40 includes prussian blue as an electron transport.

The content of the electron transporter, for example, Prussian Blue, may be 2 to 4% by weight relative to 100% by weight of the total solids of the paste forming the electrode protection and electron transport.

When the content of Prussian Blue is less than 2% by weight, it is difficult to expect a significant level of electron transport and an improvement in sensitivity corresponding thereto. In addition, when the content of Prussian Blue exceeds 4% by weight, sensitivity improvement by Prussian Blue can be expected, but due to the excessive content of Prussian Blue, the metallic electrodes constituting the electrode portion 20 are oxidized and corroded. There is a problem that can be.

Prussian Blue is a blue pigment mainly composed of potassium hexacyano iron (II) and iron (III) phosphate, and has high oxidizing properties. When the electrode protection and electron transport unit 40 including the prussian blue is formed between the electrode unit 20 and the glucose reaction unit 50, the sensitivity of the electrode may be improved, but the metallicity located below the prussian blue The electrode part 20 may be oxidized and corroded. According to an embodiment of the present invention, an electrode protection material, such as carbon, which performs an electrode protection function through oxidation prevention in addition to Prussian blue, in which the electrode protection and electron transport unit 40 performs an electron transport function, is used. Since it is configured to include, it is possible to prevent electrode corrosion and corrosion of the electrode portion 20 by Prussian blue included in the electron transport portion 40.

The results of measuring the amount of sensing current according to the content of Prussian blue constituting the electrode protection and electron transport unit 40 are disclosed in Table 1 below, and the unit of the amount of sensing current is ㎂.

Samples 1, 2, and 3 in Table 1 are cases where the molar concentrations of glucose, which is a measurement target substance, are 0.1 mM, 0.3 mM, and 0.5 mM, respectively.

Referring to Table 1, when the content of Prussian Blue constituting the electrode protection and electron transport unit 40 is 2 to 4% by weight, it can be confirmed that the sensed current amount has a significant level.

In particular, even in Sample 1, which has a relatively low glucose content compared to other samples with a molar concentration of glucose of 0.1 mM, which is a measurement target substance, the detection current amount was measured to be as low as -0.028 mA. This value is sufficient to measure glucose concentration.

The electrode protection and electron transport unit 40 may be configured to not contain a halogen component. The halogen component, in particular, when the electrode portion 20 is composed of an Ag/Palladium/Cu alloy APC, the halogen component reacts with the component of the APC to damage the electrode portion 20. . Therefore, by configuring the electrode protection and electron transport unit 30 not to contain a halogen component, it is possible to fundamentally prevent damage to the electrode unit 20 due to the halogen component, thereby securing chemical resistance and reliability of the glucose sensor. .

The content of the electrode protective material, such as carbon, may be 10 to 50% by weight with respect to 100% by weight of the total solids of the paste forming the electrode protection and electron transport portion. When the content of the electrode protective material is less than 10% by weight, the electrode protective effect may be lowered, and when it is more than 50% by weight, resistance may be increased.

The paste forming the electrode protection and electron transport portion may include an appropriate amount of a solvent in addition to the electrode protection material, the electron transporter, and the binder.

As the solvent, dimethyl ester, specifically dimethyl adipate, dimethyl glutarate, dimethyl succinate, or the like can be used.

The electrode protection and electron transport portion may have a thickness of 3 to 15 μm, for example, 8 μm. If the thickness of the electrode protection and electron transport portion is less than 3 μm, the resistance may be increased, and when it exceeds 15 μm, it may be difficult to sufficiently exhibit the role of the electron transport unit.

The glucose reaction unit 50 is formed on the electrode protection and electron transport unit 40 and is a component that reacts with glucose contained in the measurement target material.

The glucose reaction part 50 may be formed on a portion of the electrode protection and electron transport part 40.

The glucose reaction part includes an enzyme and an immobilizing agent.

In one embodiment of the present invention, the immobilizing agent serves to improve the durability of the glucose sensor by immobilizing the enzyme and preventing the enzyme from being easily wiped out.

The immobilizing agent may include a polymer compound having an amine group, a hydroxy group or a sulfonic acid group, a compound having an aldehyde group, a compound having a carboxyl group, a compound having an unhydride group, an epoxy compound, or the like, or include two or more of them. Can be.

The polymer compound having the amine group, hydroxy group or sulfonic acid group may act as a support for the enzyme.

Specifically, as the polymer compound having the amine group, hydroxy group or sulfonic acid group, chitosan, perfluorosulfonic acid resin, polypyrrole, polydopamine, polyethyleneimine, polyaniline, etc. may be exemplified. It may contain more than a species.

The compound having an aldehyde group, the compound having a carboxyl group, the compound having an unhydride group, and the epoxy compound bind the enzyme to the surface of the electrode protection and electron transport unit 40 or link the enzyme with the polymer compound acting as a support Prescribing can act as a linker.

Specifically, as the compound having an aldehyde group, glutaric aldehyde, terephthalaldehyde, anthracene-9,10-dicarboxyaldehyde, 4,4'-biphenyldicarboxyaldehyde, 1,2-benzenedicarboxaldehyde, 1 ,3-diformylbenzene, 1,4-butanedial, naphthalene dialdehyde, and the like, and the like, or these may be included alone or in combination of two or more.

Specifically, as the compound having the carboxy group, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonandaioic acid, decandioic acid, undecanedioic acid, dodecaneda Ioic acid and the like can be exemplified, and these may be used alone or in combination of two or more.

Specifically, examples of the compound having an anhydride group include acetic anhydride, butanedioic anhydride, and the like, or may include two or more of them.

Specifically, as the epoxy compound, 1,5-hexadiene diepoxide, bisphenol A diglycidyl ether, diepoxybutane, 2,2'-dimethyl-2,2'-bioxirane, dicyclo Pentadiene diepoxides and the like can be exemplified, and these may be included alone or in combination of two or more.

Preferably, the immobilizing agent may be capable of π-conjugation. When a π-conjugation-capable immobilizer is used, the saturation time of the current sensed through the electrode of the glucose sensor can be shortened. More preferably, the compound having a π-conjugable aldehyde group as the π-conjugable immobilizing agent, such as terephthalaldehyde, anthracene-9,10-dicarboxyaldehyde, 4,4'-biphenyldicarboxyaldehyde , 1,2-benzenedicarboxaldehyde, 1,3-diformylbenzene, naphthalene dialdehyde, and the like.

In particular, it is advantageous in terms of reducing the saturation time of the sensing current to use a mixture of a polymer compound serving as a support as the immobilizing agent and a compound having an aldehyde group capable of π-conjugation as a compound serving as a linker.

For example, the glucose reaction unit 50 may include glucose oxidase or glucose dehydrogenase as an enzyme.

When explaining the principle of the reaction in the glucose reaction unit 50 and the signal detection of the electrode unit 20 as follows.

When the sample to be measured is injected into the glucose sensor, glucose contained in the sample is oxidized by glucose oxidase or glucose dehydrogenase, and glucose oxidase or glucose dehydrogenase is reduced. At this time, the electron transporter oxidizes glucose oxidase or glucose dehydrogenase, and itself is reduced. The reduced electron transporter loses electrons at the surface of the electrode where a certain voltage is applied and oxidizes again electrochemically. Since the concentration of glucose in the sample is proportional to the amount of current generated in the process of oxidation of the electron transporter, the concentration of glucose can be measured by measuring the amount of current.

The ion exchange membrane 60 is formed on the glucose reaction unit 50 and passes only the component to be measured among the substances included in the sample, thereby preventing penetration of external impurity ion components and the glucose reaction unit 50 It protects the glucose oxidase or glucose dehydrogenase.

The ion exchange membrane 60 may include a cation exchange resin such as perfluorosulfonic acid resin. For example, the ion exchange membrane 60 may include Nafion or the like as a commercial product, but this is only an example, and is not limited thereto.

The total thickness of the glucose reaction unit 50 and the ion exchange membrane 60 may be 1 to 10 μm, preferably 2 to 5 μm. When the total thickness of the glucose reaction unit 50 and the ion exchange membrane 60 is less than 1 μm, the current may be reduced or it may be difficult to sufficiently exert the role of the ion exchange membrane, and when it is more than 10 μm, the reaction rate may be reduced. .

The electrode unit 20 is not illustrated, but is connected to the wiring unit. The wiring portion is formed of a plurality of electric wires extending from the electrode portion 20. The wiring unit may be connected to a sensing analysis means having a current analysis function through an electrical connection medium such as a flexible printed circuit board (FPCB). A pad region may be provided at the end of the wiring part, and the FPCB may be bonded to the pad region and electrically connected to it.

Although not illustrated in the drawing, a temperature sensor may be provided on the substrate 10. The temperature sensor is a component that is formed on the substrate 10 and measures the temperature of the environment in which glucose concentration is measured. That is, the temperature sensor transfers the current corresponding to the temperature to the IC having a current analysis function, and the IC converts the current value received from the temperature sensor to a temperature value according to a set conversion algorithm. Since the measured glucose concentration may vary depending on the temperature, the temperature can be measured along with the concentration of glucose, and the glucose concentration can be corrected according to the temperature, or the measured concentration and temperature can be matched and used. .

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. It is apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for describing the present invention, and the scope of the present invention is not limited to them.

Example One: Glucose Sensor production

A glucose sensor was manufactured in the same structure as in the embodiment of FIG. 1.

As a substrate, a PET film having a thickness of 188 μm was used, and an electrode portion was bonded to the substrate with an ultraviolet curing adhesive.

APC of 240 mm thick was used as the electrode portion, and IZO of 30 mm thick was used as the conductive oxide film.

A carbon paste was prepared by mixing 20% by weight of carbon, 1% by weight of Prussian Blue, 20% by weight of polyethylene glycol (number average molecular weight: 500,000) as a binder, and 59% by weight of dimethyl adipate as a solvent.

The carbon paste was printed on a conductive oxide film to a thickness of 8 µm to cover the conductive oxide film and the electrode portion, followed by drying to form an electrode protection and electron transport portion.

A glucose oxidase solution was prepared by dissolving chitosan (molecular weight: 310,000 to 375,000 Da) as glucose oxidase and immobilizing agent in phosphate buffered saline at concentrations of 5% and 1%, respectively.

The glucose oxidase solution was dried by dropping 1.5 µl on the electrode protection and electron transport section and drying to form a glucose reaction section, and 1.0 µl of a 1% Nafion solution was dropped on the glucose reaction section and dried to prepare an ion exchange membrane. Formed. The total thickness of the glucose reaction portion and the ion exchange membrane was 3 μm. The electrode thus prepared was used as a working electrode.

As a reference electrode corresponding to the working electrode, an Ag/AgCl paste printed on the 30 IZ thick IZO with a thickness of 8 μm was used.

Example 2: Glucose Sensor production

A glucose sensor was produced in the same manner as in Example 1, except that Nafion was used as the immobilizing agent instead of chitosan at a concentration of 1% by weight.

Example 3: Glucose Sensor production

A glucose sensor was prepared in the same manner as in Example 1, except that polyaniline (molecular weight: 100,000) was used as the immobilizing agent at a concentration of 1% by weight instead of chitosan.

Example 4: Glucose Sensor production

A glucose sensor was prepared in the same manner as in Example 1, except that terephthalaldehyde was used as the immobilizing agent in a concentration of 1% by weight instead of chitosan.

Example 5: Glucose Sensor production

A glucose sensor was prepared in the same manner as in Example 1, except that chitosan and terephthalaldehyde were used at concentrations of 0.5% and 0.5% by weight, respectively, instead of 1% by weight of chitosan as the immobilizing agent.

Example 6: Glucose Sensor production

A glucose sensor as in Example 1, except that chitosan and 4,4'-biphenyldicarboxyaldehyde were used in concentrations of 0.5% and 0.5% by weight, respectively, instead of 1% by weight of chitosan as the immobilizing agent. Was produced.

Comparative example One: Glucose Sensor production

A glucose sensor was manufactured in the same manner as in Example 1, except that the immobilizing agent was not used.

Experimental Example :

The properties of the glucose sensor prepared in the above Examples and Comparative Examples were measured by a method described below, and the results are shown in Table 2 according to the following evaluation criteria.

(1) Durability

The initial value was obtained by measuring the current value with a 0.2 mM glucose solution using a glucose sensor by applying a voltage of -0.1 V to a 630e device of CH Instruments.

Thereafter, the glucose sensor was left at room temperature for 500 hours, and then the current value was measured in the same manner as the above conditions to calculate the rate of change of the current value compared to the initial measurement value.

<Evaluation criteria>

OK: When the current value is less than 30% compared to the initial measured value

NG: When the current value is reduced by more than 30% compared to the initial measured value

(2) Sensing current saturation time

The time at which the current value of the glucose sensor stabilized was measured by applying a voltage of -0.1 V to a 630e device of CH Instruments.

division durability Sensing current saturation time (sec) Example 1 OK 500 Example 2 OK 500 Example 3 OK 500 Example 4 OK 400 Example 5 OK 300 Example 6 OK 300 Comparative Example 1 NG 2000

As shown in Table 2, it was found that the glucose sensors of Examples 1 to 6 using the immobilizing agent were superior in durability and shortened the saturation time of the current compared to the glucose sensor of Comparative Example 1 without the immobilizing agent.

Since the specific parts of the present invention have been described in detail above, it is obvious that for those skilled in the art to which the present invention pertains, this specific technology is only a preferred embodiment, and the scope of the present invention is not limited thereto. Do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

10: substrate 20: electrode portion
30: conductive oxide film 40: electrode protection and electron transport
50: glucose reaction unit 60: ion exchange membrane

Claims (15)

Board;
An electrode portion formed on the substrate;
An electrode protection and electron transport unit formed to cover the electrode unit on the electrode unit; And
It includes a glucose reaction portion formed on the electrode protection and electron transport,
The glucose reaction unit is a glucose sensor comprising an enzyme and an immobilizing agent. The glucose sensor of claim 1, further comprising an ion exchange membrane formed on the glucose reaction unit. The glucose sensor of claim 1, wherein the electrode protection and electron transport unit comprises an electrode protection material, an electron transporter, and a binder. The glucose sensor according to claim 3, wherein the electrode protective material comprises carbon. The glucose sensor of claim 3, wherein the electron transporter comprises prussian blue. The method of claim 1, wherein the immobilizing agent includes at least one selected from the group consisting of a polymer compound having an amine group, a hydroxyl group or a sulfonic acid group, a compound having an aldehyde group, a compound having a carboxyl group, a compound having an unhydride group, and an epoxy compound. Glucose sensor. The method of claim 6, wherein the polymer compound having an amine group, hydroxy group or sulfonic acid group includes at least one selected from the group consisting of chitosan, perfluorosulfonic acid resin, polypyrrole, polydopamine, polyethyleneimine and polyaniline. Glucose sensor. The compound according to claim 6, wherein the compound having an aldehyde group is glutaric aldehyde, terephthalaldehyde, anthracene-9,10-dicarboxyaldehyde, 4,4'-biphenyldicarboxyaldehyde, 1,2-benzenedicarboxyaldehyde. , 1,3-diformylbenzene, 1,4-butanedial and naphthalene dialdehyde. The compound of claim 6, wherein the compound having a carboxy group is propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonandaioic acid, decandioic acid, undecanedioic acid, and Glucose sensor comprising at least one selected from the group consisting of dodecanedioic acid. The glucose sensor according to claim 6, wherein the compound having an anhydride group comprises at least one selected from the group consisting of acetic anhydride and butanedioic anhydride. The method of claim 6, wherein the epoxy compound is 1,5-hexadiene diepoxide, bisphenol A diglycidyl ether, diepoxybutane, 2,2'-dimethyl-2,2'-bioxirane and Glucose sensor comprising at least one selected from the group consisting of dicyclopentadiene diepoxide. The glucose sensor of claim 1, wherein the immobilizing agent is capable of π-conjugation. The glucose sensor according to claim 1, wherein the immobilizing agent is a compound having an aldehyde group capable of π-conjugation. The glucose sensor according to claim 1, wherein the immobilizing agent comprises a polymer compound having an amine group, a hydroxyl group or a sulfonic acid group, and a compound having an aldehyde group capable of π-conjugation. The glucose sensor of claim 1, wherein the enzyme comprises glucose oxidase or glucose dehydrogenase.

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