KR20190009973A - Glucose sensor - Google Patents

Abstract

The present invention relates to a glucose sensor. The glucose sensor comprises: a substrate; a conductive electrode unit formed on the substrate; a Prussian blue layer formed on the electrode unit and increasing sensibility of the electrode unit; and a glucose reaction unit formed on the Prussian blue layer. The electrode unit has a single layer structure including dissimilar metals, and a difference in standard reduction potentials between the dissimilar metals constituting the electrode unit is 0.05 V or more and 0.5 V or less. Accordingly, a metal component constituting the electrode unit corrodes by the Prussian blue layer increasing electrical sensitivity of the electrode unit constituting the glucose sensor, thereby preventing or delaying reduction in sensor performance.

Description

Glucose sensor {GLUCOSE SENSOR}

The present invention relates to a glucose sensor and a manufacturing method thereof. More particularly, the present invention relates to a glucose sensor capable of preventing or delaying deterioration of sensor performance due to erosion of a metal component constituting an electrode portion by a prussian blue layer that increases the electrical sensitivity of the electrode portion.

Glucose is a broad nutrient source of most organisms and plays a fundamental role in energy supply, carbon storage, biosynthesis, and carbon skeleton and cell wall formation. Glucose sensor, which measures glucose concentration through potential difference or current measurement, Is being actively studied.

Most studies on glucose sensors are based on the fixation of enzymes such as glucose oxidase or glucose dehydrogenase, which catalyze the oxidation of glucose to gluconolactone.

On the other hand, according to the prior art relating to the glucose sensor, a prussian blue layer is formed on the electrode in order to increase the electrical sensitivity of the electrode. Since this Prussian blue layer is highly oxidative, However, there is a problem that the metal component constituting the electrode is oxidized by the Prussian blue layer and corroded.

Korean Patent Registration No. 10-1107506 (registered date: January 12, 2012, name: glucose sensor equipped with titanium dioxide-graphene complex)

The present invention provides a glucose sensor capable of preventing or delaying deterioration of sensor performance due to erosion of a metal component constituting an electrode part by a Prussian blue layer that increases the electrical sensitivity of the electrode part.

According to a first aspect of the present invention, there is provided a glucose sensor comprising a substrate, a conductive electrode portion formed on the substrate, a prussian blue layer formed on the electrode portion to increase the sensitivity of the electrode portion, and a glucose reaction part formed on the Prussian blue layer, wherein the electrode part has a single layer structure including a dissimilar metal, and the difference in the standard reduction potential between dissimilar metals constituting the electrode part is 0.05V or more and 0.5 V or less.

According to a second aspect of the present invention, there is provided a glucose sensor comprising a substrate, a conductive electrode part formed on the substrate, a Prussian blue layer formed on the electrode part to increase the sensitivity of the electrode part, The electrode portion has a two-layer structure, and the thickness of the upper layer constituting the electrode portion is 200 nm or more and 10um or less.

In the glucose sensor according to the second aspect of the present invention, the upper layer and the lower layer constituting the electrode portion are made of a single metal, and the difference in the standard reduction potential between the metal forming the upper layer and the metal forming the lower layer is 0.05V or more and 0.5 V or less.

In the glucose sensor according to the first aspect of the present invention, when the electrode portion has a single layer structure including dissimilar metals, the electrode portion may include graphite, platinum, titanium, silver, , Nickel, copper, tin, molybdenum, cobalt, and the like. The present invention is not limited to these examples.

In the glucose sensor according to the second aspect of the present invention, when the electrode part has a two-layer structure, the upper or lower layer constituting the electrode part may be formed of graphite, platinum, titanium, silver, , Nickel, copper, tin, molybdenum, cobalt, and the like. The present invention is not limited to these examples.

In the glucose sensor according to the second aspect of the present invention, the electronegativity of the upper layer constituting the electrode portion is larger than that of the lower layer.

The glucose sensor according to both aspects of the present invention further comprises a cation exchange membrane formed on the glucose reaction unit.

In the glucose sensor according to both aspects of the present invention, the glucose reaction unit may include a glucose oxidase or a glucose dehydrogenase.

According to the present invention, there is provided the glucose sensor capable of preventing or delaying the deterioration of the sensor performance due to corrosion of the metal component constituting the electrode part by the Prussian blue layer which increases the electrical sensitivity of the electrode part.

1 is a conceptual cross-sectional view of a glucose sensor according to a first embodiment of the present invention,
2 is a conceptual cross-sectional view of a glucose sensor according to a second embodiment of the present invention.

It is to be understood that the specific structural or functional description of embodiments of the present invention disclosed herein is for illustrative purposes only and is not intended to limit the scope of the inventive concept But may be embodied in many different forms and is not limited to the embodiments set forth herein.

The embodiments according to the concept of the present invention can make various changes and can take various forms, so that the embodiments are illustrated in the drawings and described in detail herein. It should be understood, however, that it is not intended to limit the embodiments according to the concepts of the present invention to the particular forms disclosed, but includes all modifications, equivalents, or alternatives falling within the spirit and scope of the invention.

The terms first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The terms may be named for the purpose of distinguishing one element from another, for example, without departing from the scope of the right according to the concept of the present invention, the first element may be referred to as a second element, The component may also be referred to as a first component.

It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, . On the other hand, when an element is referred to as being "directly connected" or "directly connected" to another element, it should be understood that there are no other elements in between. Other expressions that describe the relationship between components, such as "between" and "between" or "neighboring to" and "directly adjacent to" should be interpreted as well.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like are used to specify that there are features, numbers, steps, operations, elements, parts or combinations thereof described herein, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the meaning of the context in the relevant art and, unless explicitly defined herein, are to be interpreted as ideal or overly formal Do not.

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

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

1, a glucose sensor according to a first embodiment of the present invention includes a substrate 10, an electrode unit 20, a prussian blue layer 40, a glucose reaction unit 50, and a cation exchange membrane 60 .

The substrate 10 provides a structural base of the components that make up the glucose sensor.

For example, the substrate 10 may have rigid or flexible characteristics and may be embodied in the form of a substrate film having flexible characteristics. As a specific example, when the substrate 10 is implemented in the form of a base film, applicable base films include polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; Cellulose-based resins such as diacetylcellulose and triacetylcellulose; Polycarbonate resin; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin resins such as polyethylene, polypropylene, cyclo- or norbornene-structured polyolefins, ethylene-propylene copolymers; Vinyl chloride resin; Amide resins such as nylon and aromatic polyamide; Imide resin; Polyether sulfone type resin; Sulfone based resin; Polyether ether ketone resin; A sulfided polyphenylene resin; Vinyl alcohol-based resin; Vinylidene chloride resins; Vinyl butyral resin; Allylate series resin; Polyoxymethylene type resin; Epoxy resin, and the like, and a film composed of the blend of the thermoplastic resin may also be used. Further, a film made of a thermosetting resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, or silicone or a film made of an ultraviolet curable resin may be used. The thickness of such a transparent optical film can be suitably determined, but in general, it can be determined to be 1 to 500 占 퐉 in consideration of workability such as strength and handling property, thin layer property, and the like. Particularly preferably 1 to 300 mu m, and more preferably 5 to 200 mu m.

Such a base film may contain one or more suitable additives. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment and a colorant. The base film may be a structure including various functional layers such as a hard coating layer, an antireflection layer, and a gas barrier layer on one side or both sides of the film. The functional layer is not limited to the above, and may include various functional layers can do.

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

The electrode unit 20 is formed on the substrate 10 and senses an electrical signal generated by a reaction between a substance included in the glucose reaction unit 50 described later and glucose contained in the measurement target substance. For example, the substance to be measured may be, but is not limited to, blood, sweat, body fluid, etc. of the human body.

The electrode portion 20 has a single layer structure including a dissimilar metal, and the difference in standard reduction potential between dissimilar metals constituting the electrode portion 20 is 0.05 V or more and 0.5 V or less.

The standard reduction potential is the standard used to determine the extent of the reduction reaction under standard conditions of 25 ° C and 1 atmosphere. A standard hydrogen electrode is used as an oxidation electrode, and an electrode where a reaction takes place is set as a reduction electrode, and the standard reduction potential is measured. This standard reduction potential is measured with a standard hydrogen electrode at 0.00 V. If the potential of the reducing electrode is positive, the reductivity is greater than that of hydrogen ion. If the potential of the reducing electrode is negative, the reductivity is smaller than that of hydrogen ion, and the smaller the value, the greater the ionization tendency.

In the glucose sensor according to the first embodiment of the present invention, when the difference in the standard reduction potential between dissimilar metals constituting the electrode unit 20 is 0.05 V or more and 0.5 V or less, A phenomenon that the electrode unit 20 is oxidized and corroded by the Prussian blue layer 40 can be reduced. Corrosion caused by oxidization of the electrode portion 20 by the Prussian blue layer 40 occurs first in the metal having a low standard reduction potential and also in the metal having a high standard reduction potential over time. Here, if the difference in the standard reduction potential between the dissimilar metals constituting the electrode unit 20 is set to a relatively small value such as 0.05 V or more and 0.5 V or less, the electrode unit 20 by the Prussian blue layer 40, Can be delayed.

For example, when the electrode portion 20 has a single layer structure including a dissimilar metal, the electrode portion 20 may be formed of graphite, platinum, titanium, silver, nickel the electrode portion 20 may include at least one selected from the group consisting of copper, nickel, copper, tin, molybdenum, and cobalt. And any material having excellent electrical conductivity and corrosion resistance can be applied.

The Prussian blue layer 40 is formed on the electrode part 20 and functions to increase the electrical sensitivity of the electrode part 20. [

This Prussian blue layer 40 is a blue pigment mainly composed of potassium hexacyanoferrate (II) iron (III) oxide, and has a high oxidizing property. When the Prussian blue layer 40 is formed between the electrode unit 20 and the glucose reaction unit 50, the sensitivity of the electrode unit 20 can be improved. However, The metallic electrode portion 20 may be oxidized and corroded. In the first embodiment of the present invention, as described above, in order to prevent deterioration of the sensor performance due to corrosion of the electrode unit 20, the electrode unit 20 is constructed as described above.

The glucose reaction unit 50 is formed on the Prussian blue layer 40 and is a component that reacts with glucose contained in the measurement target substance.

For example, the glucose reaction unit 50 may include a glucose oxidase or a glucose dehydrogenase.

The reaction in the glucose reaction unit 50 and the signal detection principle of the electrode unit 20 will be described below as an example.

When a sample to be measured is injected into a glucose sensor, the glucose contained in the sample is oxidized by a glucose oxidase or a glucose dehydrogenase, and a glucose oxidase or a glucose dehydrogenase is reduced. At this time, the electron transfer mediator oxidizes glucose oxidase or glucose dehydrogenase and itself is reduced. The reduced electron transfer mediator loses electrons at the surface of the electrode to which a constant voltage is applied and is electrochemically reoxidized. The glucose concentration in the sample is proportional to the amount of current generated in the course of the oxidation of the electron transport mediator. Thus, the glucose concentration can be measured by measuring this amount of current.

The cation exchange membrane 60 is formed on the glucose reaction unit 50, and allows only the component to be measured to pass through among the substances contained in the sample. Such a cation exchange membrane 60 has negative charge and selectively permeates cations.

2 is a conceptual cross-sectional view of a glucose sensor according to a second embodiment of the present invention.

2, the glucose sensor according to the second embodiment of the present invention includes a substrate 10, an electrode unit 30, a Prussian blue layer 40, a glucose reaction unit 50, and a cation exchange membrane 60 .

The substrate 10 provides a structural base of the components that make up the glucose sensor.

Since the structure and function of the substrate 10 of the second embodiment are the same as those of the substrate 10 of the first embodiment, the duplicated description will be omitted.

The electrode portion 30 has a two-layer structure, and the thickness of the upper layer 34 constituting the electrode portion 30 is 200 nm or more and 10um or less.

If the upper layer 34 directly contacting the Prussian blue layer 40 is configured to have a thickness of 200 nm or more and 10um or less in thickness as described above, even if the upper layer 34 is oxidized and corroded by the Prussian blue layer 40, The thicker thickness of the upper layer 34 may delay the significant degradation of the electrode 30 time point.

For example, when the electrode portion 30 has a two-layer structure, the upper layer 34 and the lower layer 32 constituting the electrode portion 30 are made of a single metal, and the upper layer 34 and the lower layer The difference in the standard reduction potential between the metals constituting the first electrode 32 and the second electrode 32 may be 0.05 V or more and 0.5 V or less.

In the glucose sensor according to the second embodiment of the present invention, the difference in standard reduction potential between the metal forming the upper layer 34 constituting the electrode section 30 and the metal constituting the lower layer 32 is 0.05 V or more and 0.5 V or less It is possible to reduce the phenomenon that the electrode unit 30 is oxidized and corroded by the prussian blue layer 40 provided to increase the sensitivity of the electrode unit 30. [ Corrosion caused by oxidization of the electrode portion 30 by the Prussian blue layer 40 occurs first in a metal having a low standard potential and also in a metal having a high standard potential as time goes by. If the difference in the standard reduction potential between the metal forming the upper layer 34 constituting the electrode unit 20 and the metal constituting the lower layer 32 is set to a relatively small value such as not less than 0.05 V and not more than 0.5 V, The starting point of oxidation of the electrode section 20 by the Russian blue layer 40 can be delayed.

For example, when the electrode unit 30 has a two-layer structure, the upper layer 34 or the lower layer 32 constituting the electrode unit 30 may be formed of graphite, platinum, titanium, and may include at least one member selected from the group consisting of silver, nickel, copper, tin, molybdenum, and cobalt, The material applicable to the upper layer 34 or the lower layer 32 is not limited thereto, and any material having excellent electrical conductivity and corrosion resistance may be applied.

For example, the electronegativity of the upper layer 34 constituting the electrode portion 30 to delay oxidation by the Prussian blue layer 40 may be configured to be greater than the electronegativity of the lower layer 32 .

The Prussian blue layer 40 is formed on the electrode part 30 and functions to increase the electrical sensitivity of the electrode part 30. [

This Prussian blue layer 40 is a blue pigment mainly composed of potassium hexacyanoferrate (II) iron (III) oxide, and has a high oxidizing property. When the Prussian blue layer 40 is formed between the electrode unit 30 and the glucose reaction unit 50, the sensitivity of the electrode unit 30 can be improved. However, The metallic electrode portion 30 may be oxidized and corroded. In the first embodiment of the present invention, as described above, in order to prevent deterioration of the sensor performance due to corrosion of the electrode unit 30, the electrode unit 30 is constructed as described above.

The glucose reaction unit 50 is formed on the Prussian blue layer 40 and is a component that reacts with glucose contained in the measurement target substance.

For example, the glucose reaction unit 50 may include a glucose oxidase or a glucose dehydrogenase.

The reaction in the glucose reaction unit 50 and the signal detection principle of the electrode unit 30 will be described below as an example.

When a sample to be measured is injected into a glucose sensor, the glucose contained in the sample is oxidized by a glucose oxidase or a glucose dehydrogenase, and a glucose oxidase or a glucose dehydrogenase is reduced. At this time, the electron transfer mediator oxidizes glucose oxidase or glucose dehydrogenase and itself is reduced. The reduced electron transfer mediator loses electrons at the surface of the electrode to which a constant voltage is applied and is electrochemically reoxidized. The glucose concentration in the sample is proportional to the amount of current generated in the course of the oxidation of the electron transport mediator. Thus, the glucose concentration can be measured by measuring this amount of current.

The cation exchange membrane 60 is formed on the glucose reaction unit 50, and allows only the component to be measured to pass through among the substances contained in the sample. Such a cation exchange membrane 60 has negative charge and selectively permeates cations.

As described above in detail, according to the present invention, it is possible to prevent or delay the phenomenon that the metal component constituting the electrode part is corroded by the Prussian blue layer which increases the electrical sensitivity of the electrode part constituting the glucose sensor, There is an effect.

10: substrate
20, 30:
32: Lower layer
34: Upper layer
40: Prussian blue floor
50: glucose reaction part
60: Cation exchange membrane

Claims (8)

Board;
A conductive electrode portion formed on the substrate;
A prussian blue layer formed on the electrode portion to increase the sensitivity of the electrode portion; And
And a glucose reaction unit formed on the Prussian blue layer,
Wherein the electrode portion has a single layer structure including a dissimilar metal,
Wherein the difference in standard reduction potential between dissimilar metals constituting the electrode portion is 0.05 V or more and 0.5 V or less. Board;
A conductive electrode portion formed on the substrate;
A prussian blue layer formed on the electrode portion and enhancing sensitivity of the electrode portion; And
And a glucose reaction unit formed on the Prussian blue layer,
Wherein the electrode portion has a two-layer structure,
Wherein the thickness of the upper layer constituting the electrode portion is 200 nm or more and 10um or less. 3. The method of claim 2,
Wherein the upper and lower layers constituting the electrode portion are made of a single metal,
Wherein the difference in standard reduction potential between the metal forming the upper layer and the metal forming the lower layer is 0.05 V or more and 0.5 V or less. The method according to claim 1,
When the electrode portion has a single layer structure including different metals,
The electrode portion may be formed of a material selected from the group consisting of graphite, platinum, titanium, silver, nickel, copper, tin, molybdenum, and cobalt ≪ / RTI > 3. The method of claim 2,
When the electrode portion has a two-layer structure,
The upper or lower layer constituting the electrode portion may be formed of at least one selected from the group consisting of graphite, platinum, titanium, silver, nickel, copper, tin, molybdenum, and cobalt. < RTI ID = 0.0 > 8. < / RTI > 3. The method of claim 2,
And the electronegativity of the upper layer constituting the electrode portion is larger than that of the lower layer. 3. The method according to claim 1 or 2,
Wherein the glucose sensor further comprises a cation exchange membrane formed on the glucose reaction unit. 3. The method according to claim 1 or 2,
Wherein the glucose reaction unit comprises a glucose oxidase or a glucose dehydrogenase.

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