CN114184661A - Electrochemical sensor and manufacturing method thereof - Google Patents

Abstract

The embodiment of the application provides an electrochemical sensor and a manufacturing method thereof, which relate to the technical field of electrochemical analysis and comprise a substrate and an electrode arranged on the substrate; the electrodes comprise a power supply electrode and a plurality of working electrodes, the surfaces of the working electrodes are respectively provided with a plurality of reagent enzymes, and the reagent enzymes on the surface of each working electrode are different; wherein, the power supply electrode is positioned in the first area of the substrate; the plurality of working electrodes are positioned in the second area of the substrate; the second area comprises a plurality of sub-areas which are mutually independent on the substrate, and the plurality of working electrodes are respectively positioned in different sub-areas; the electrode structure is characterized by further comprising a guide layer, wherein the guide layer is made of paper materials, is located above the electrode and covers the first area and the second area. Through the electrochemical sensor and the electrochemical detector provided by the embodiment of the application, the condition of mutual interference between working electrodes can be reduced, and the accuracy of a detection result is improved.

Description

Electrochemical sensor and manufacturing method thereof

Technical Field

The embodiment of the application relates to the technical field of electrochemical analysis, in particular to an electrochemical sensor and a manufacturing method thereof.

Background

An electrochemical enzyme sensor, i.e., an enzyme biosensor, has a basic structural unit composed of a substance-recognizing element (immobilized enzyme membrane) and a signal converter (substrate electrode). When an enzymatic reaction occurs on the enzyme membrane, the resulting electroactive species is responded to by the matrix electrode. The function of the substrate electrode is to convert chemical signals into electrical signals for detection.

At present, an electrochemical sensor generally includes a plurality of working electrodes, wherein different specific enzymes are immobilized on the working electrodes, and the different specific enzymes can catalyze corresponding analytes in a liquid to react, and generate reactants to operate the working electrodes. Therefore, the electrochemical sensor can detect a plurality of components in the liquid to be detected.

However, since the products of the reactions of different analytes catalyzed by different specific enzymes may be the same and all the working electrodes are located on the same substrate, when the working electrodes are closely spaced, the working electrodes may interfere with each other, resulting in errors in the detection of the components in the liquid.

Disclosure of Invention

The embodiment of the application provides an electrochemical sensor and a manufacturing method thereof, aiming at reducing the mutual interference between working electrodes and improving the accuracy of a detection result.

A first aspect of embodiments of the present application provides an electrochemical sensor, including a substrate and an electrode disposed on the substrate;

the electrodes comprise a power supply electrode and a plurality of working electrodes, the surfaces of the working electrodes are respectively provided with a plurality of reagent enzymes, and the reagent enzymes on the surfaces of the working electrodes are different;

wherein the power supply electrode is located in a first region of the substrate; the plurality of working electrodes are positioned in a second area of the substrate;

the second region comprises a plurality of sub-regions which are mutually independent on the substrate, and the plurality of working electrodes are respectively positioned in different sub-regions;

still include the guide layer, the guide layer is the paper material, the guide layer is located the top of electrode, just the guide layer covers first region with the second area, just an edge of guide layer extends to the edge setting of base plate.

Optionally, the material of the guide layer includes: filter paper, chromatography paper or blotting paper.

Optionally, the plurality of working electrodes are located on one or both sides of the power supply electrode;

alternatively, the plurality of working electrodes are arranged at even intervals along the circumferential direction of the power supply electrode.

Optionally, the width of the guide layer in the second region is 10 μm-5 mm.

Optionally, the power supply electrode comprises: an active electrode.

Optionally, the power supply electrode comprises: a counter electrode and a reference electrode.

A second aspect of embodiments of the present application provides a method for manufacturing an electrochemical sensor, the method including: providing a substrate;

forming a power supply electrode and a plurality of working electrodes on a substrate by a printing process, and drying;

covering the leads of the power supply electrode and the working electrodes with insulating slurry, and drying;

printing reagent enzyme on the working electrodes through a printing process, and drying;

a guiding layer covers the power supply electrode and the plurality of working electrodes.

Has the advantages that:

the application provides an electrochemical sensor and a manufacturing method thereof, wherein a counter electrode, a reference electrode and a plurality of working electrodes are arranged on a substrate, the counter electrode and the reference electrode are positioned in a first area on the substrate, the working electrodes are positioned in a second area on the substrate, meanwhile, each working electrode is positioned in different sub-areas in the second area, and then a paper guide layer is arranged on the substrate to enable the guide layer to completely cover the first area and the second area of the substrate; when the electrochemical sensor is used for detection, liquid drops to be detected enter the guide layer from the edge of the substrate, the liquid to be detected can diffuse on the guide layer due to the diffusivity of the liquid on the paper material, and finally diffuse to the guide layer of each sub-region in the second region, and at the moment, the reagent enzyme on the working electrode can react with the corresponding component in the liquid to be detected.

Because each working electrode is positioned in different sub-regions, and the sub-regions are mutually independent, reactants generated by the reagent enzyme reaction cannot directly move to the positions of other working electrodes, so that the mutual interference among different working electrodes is reduced, and the detection accuracy of the electrochemical sensor is improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments of the present application will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without inventive exercise.

FIG. 1 is a schematic diagram of an electrochemical sensor according to an embodiment of the present disclosure;

FIG. 2 is a schematic side view of an electrochemical sensor according to an embodiment of the present disclosure;

FIG. 3 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 4 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 5 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 6 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 7 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 8 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 9 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 10 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 11 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 12 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 13 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 14 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 15 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 16 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 17 is a schematic structural diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 18 is a schematic diagram of another electrochemical sensor according to an embodiment of the present application;

FIG. 19 is a flow chart illustrating steps in a method of manufacturing an electrochemical sensor according to an embodiment of the present application;

FIG. 20 is a flowchart illustrating steps of a method for fabricating a guiding layer according to an embodiment of the present disclosure;

fig. 21 is a flowchart illustrating steps of another method for manufacturing a guiding layer according to an embodiment of the present disclosure.

Description of reference numerals: 1. a substrate; 11. a first region; 12. a second region; 121. a sub-region; 2. a power supply electrode; 21. a counter electrode; 22. a reference electrode; 3. a working electrode; 4. a guide layer; 5. an insulating layer.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Example one

Referring to fig. 1, an electrochemical sensor disclosed in this embodiment of the present application includes a substrate 1 and electrodes disposed on the substrate 1, and the electrochemical sensor disclosed in this embodiment of the present application is mainly directed to detecting various components in a liquid.

Specifically, the substrate 1 may be made of polyester resin or polyimide.

Referring to fig. 1, the electrodes include a power supply electrode 2 and a plurality of working electrodes 3, and the power supply electrode 2 functions to connect a circuit and stabilize a voltage. Moreover, the surface of the electrode detection end of each working electrode 3 is provided with a reagent enzyme, the reagent enzyme can react with a corresponding analyte in the liquid to be detected, a product is generated through the reaction of the reagent enzyme, and the product can be subjected to oxidation or reduction reaction on the working electrode 3 on the corresponding sensor to generate the change of an electric signal; meanwhile, reagent enzymes on each working electrode 3 are different, so that multiple components in the liquid to be detected can be detected by using one electrochemical sensor, and the detection efficiency of the electrochemical sensor can be effectively improved; of course, a biosensor may be used to detect a component, so that the sensors of the working electrodes 3 all generate changes of electrical signals, and the detection result obtained through calculation and statistics is more accurate. Referring to fig. 2, leads of the power supply electrode 2 and the working electrode 3 are covered with an insulating layer 5.

Specifically, referring to fig. 1, the substrate 1 includes a first region 11 and a second region 12, the power supply electrode is located in the first region 11 of the substrate 1, and the working electrode 3 is located in the second region 12 of the substrate 1, where it should be noted that the first region 11 and the second region 12 are not a specific space formed on the substrate 1, but are a partition of the substrate 1 itself, and the sizes of the first region 11 and the second region 12 are set according to actual needs.

Further, referring to fig. 1, the second region 12 further includes a plurality of sub-regions 121, each sub-region 121 is independent from another sub-region 121, that is, on the substrate 1, the positions of each sub-region 121 are spaced apart from each other and are not related, and the sizes of each sub-region 121 may be the same or different; the number of sub-regions 121 corresponds to the number of working electrodes 3, and each working electrode 3 is located within one sub-region 121.

Referring to fig. 1, the electrochemical sensor further includes a guiding layer 4, the guiding layer 4 is made of a paper material, the paper material is a porous material, after the liquid to be detected is dropped on the guiding layer 4, the guiding layer 4 of the paper material generates capillary force on the liquid to be detected, so that the liquid to be detected can be diffused on the guiding layer 4, and the width of the guiding layer in the second area is 10 μm to 5 mm.

Fig. 2 is a schematic side view showing the structure of the electrochemical sensor, and as shown in fig. 2, the guide layer 4 is located above the power electrode 2 and the working electrode 3, and the guide layer 4 covers the first region 11 and the second region 12 of the substrate 1, and as shown in fig. 1, the shape of the entire guide layer 4 is the same as the shape formed by the first region 11 and the second region 12, and the area of the guide layer 4 also corresponds to the area included in the first region 11 and the second region 12. And one edge of the guide layer 4 extends to the edge of the substrate 1 so that the liquid to be detected can enter the guide layer 4 therefrom.

It should be noted that fig. 2 is only a schematic diagram of the structure of the electrochemical sensor, and in practical applications, the thicknesses of the power electrode 2, the working electrode 3, and the guide layer 4 are all in the order of micrometers, so that the guide layer 4 is actually attached to the substrate 1.

When the electrochemical sensor is used, liquid to be detected enters the guide layer 4 from the edge of the substrate 1, and the liquid can diffuse on the guide layer 4 automatically, so that the liquid can gradually diffuse from the guide layer 4 in the first region 11 to the guide layer 4 in each sub-region 121 in the second region 12, when the liquid to be detected diffuses to the position of the electrode detection end of each working electrode 3, corresponding components in the liquid to be detected can react with different reagent enzymes on each working electrode 3, products generated by the reagent enzymes and the corresponding components in the liquid to be detected can enable the working electrodes 3 to generate electric signals, and therefore detection of various components in the liquid to be detected is achieved. Of course, if there is no component in the liquid to be detected that reacts enzymatically with a certain reagent, the corresponding working electrode 3 will not generate an electrical signal.

Since each sub-area 121 is independent from each other and each sub-area 121 is covered with the guide layer 4, the reagent enzyme and the reactant generated by the corresponding component in the liquid to be detected cannot easily move to the positions of other working electrodes 3 through the guide layer 4, so that the reactants generated by the reaction of different reagent enzymes are the same, the mutual interference between each working electrode 3 is reduced, and the accuracy of the detection result is improved.

When the method is applied specifically, the guide layer 4 can be fixed on the substrate 1 by means of glue adhesion, and the guide layer 4 is integrally cut and formed.

In one embodiment, the material of the guiding layer 4 can be selected from filter paper, chromatography paper or blotting paper.

The filter paper, the chromatographic paper and the blotting paper have strong water absorbability, and can better diffuse the liquid on the guide layer 4.

The electrode material of the working electrode 3 may be gold, platinum, carbon, or a composite material containing gold, platinum, or carbon.

The power supply electrode 2 includes two cases.

Referring to fig. 7, in the first case, the power electrode 2 only comprises the active electrode 21, and the active electrode 21 can simultaneously perform the functions of connecting the circuit and stabilizing the voltage, and at this time, the material of the active electrode 21 is Ag/AgCl, wherein the ratio of silver to silver chloride is 1:1, 6:4 or 7: 3.

Referring to fig. 3, in the second case, the power supply electrode 2 includes a counter electrode 21 and a reference electrode 22, wherein the counter electrode 21 functions as a communication circuit, and the reference electrode 22 functions as a stable voltage, and in this case, the material of the counter electrode 21 is the same as that of the working electrode 3.

The reference electrode 22 is made of Ag/AgCl, wherein the ratio of silver to silver chloride is 1:1, 6:4 or 7: 3.

The working electrodes are positioned on one side or two sides of the power supply electrode; alternatively, the plurality of working electrodes are arranged at regular intervals along the circumferential direction of the power supply electrode.

In one embodiment, referring to fig. 3, the power electrode 2 includes a counter electrode 21 and a reference electrode 22, three working electrodes 3 are provided, electrode detection ends of the three working electrodes 3 are located on the same straight line on the substrate 1, correspondingly, three sub-regions 121 are formed on the substrate 1, each sub-region 121 is in a long strip shape, and the three long strip-shaped sub-regions 121 are parallel to each other.

In one embodiment, referring to fig. 4, the power supply electrode includes a counter electrode 21 and a reference electrode 22, three working electrodes 3 are provided, electrode detection ends of the three working electrodes 3 are located on the same straight line on the substrate 1, and correspondingly, three sub-regions 121 are formed on the substrate 1, but the shape of each sub-region 121 is different, and the position of each sub-region 121 is also different.

In one embodiment, referring to fig. 5, the power electrode 2 includes a counter electrode 21 and a reference electrode 22, three working electrodes 3 are provided, electrode detection ends of the three working electrodes 3 are located at different positions on the substrate 1, correspondingly, three sub-regions 121 are formed on the substrate 1, and shapes and positions of the three sub-regions 121 are different.

In one embodiment, referring to fig. 6, the counter electrode 21, the reference electrode 22, and the working electrode 3 may also be disposed in a vertical direction on the substrate 1.

In one embodiment, as shown with reference to fig. 7, the power supply electrode 2 comprises only the active electrode 21; the number of the working electrodes 3 is three, the electrode detection ends of the three working electrodes 3 are located on the same straight line on the substrate 1, correspondingly, three sub-regions 121 are formed on the substrate 1, each sub-region 121 is in a long strip shape, and the three long strip-shaped sub-regions 121 are parallel to each other.

In one embodiment, as shown with reference to fig. 8, the power supply electrode 2 comprises only the active electrode 21; the number of the working electrodes 3 is three, the electrode detection ends of the three working electrodes 3 are located on the same straight line on the substrate 1, and correspondingly, three sub-regions 121 are formed on the substrate 1, but the shape of each sub-region 121 is different, and the position of each sub-region 121 is also different.

In one embodiment, as shown with reference to fig. 9, the power supply electrode 2 comprises only the active electrode 21; the number of the working electrodes 3 is three, the electrode detection ends of the three working electrodes 3 are located at different positions on the substrate 1, correspondingly, three sub-regions 121 are formed on the substrate 1, and the shapes and the positions of the three sub-regions 121 are different.

In one embodiment, as shown with reference to fig. 10, the power supply electrode 2 comprises only the active electrode 21; the number of the working electrodes 3 is three, and the three working electrodes 3 are arranged in the vertical direction on the substrate 1.

In one embodiment, as shown with reference to fig. 11, the power supply electrode 2 comprises only the active electrode 21; the number of the working electrodes 3 is four, and the four working electrodes 3 are respectively located on both sides of the action electrode 21.

In one embodiment, as shown with reference to fig. 12, the power supply electrode 2 comprises only the active electrode 21; the number of the working electrodes 3 is four, and the four working electrodes 3 are uniformly distributed along the circumferential direction of the action electrode 21.

In one embodiment, as shown with reference to fig. 13, the power supply electrode 2 comprises only the active electrode 21; the working electrodes 3 are provided with six in total, and the six working electrodes 3 are uniformly distributed along the circumferential direction of the action electrode 21.

In one embodiment, as shown with reference to fig. 14, the power supply electrode 2 comprises only the active electrode 21; twelve working electrodes 3 are arranged, and twelve working electrodes 3 are uniformly distributed along the circumferential direction of the action electrode 21 in two circles.

In other embodiments, three, four, or more turns of the working electrode 3 may be provided.

In one embodiment, referring to fig. 15, the power electrode 2 includes a counter electrode 21 and a reference electrode 22; the number of the working electrodes 3 is four, and the four working electrodes 3 are respectively positioned on two sides of the counter electrode 21 and the reference electrode 22.

In one embodiment, referring to fig. 16, the power electrode 2 includes a counter electrode 21 and a reference electrode 22; the number of the working electrodes 3 is four, and the four working electrodes 3 are uniformly distributed along the circumferential direction of the counter electrode 21 and the reference electrode 22.

In one embodiment, referring to fig. 17, the power electrode 2 includes a counter electrode 21 and a reference electrode 22; six working electrodes 3 are provided in total, and the six working electrodes 3 are uniformly distributed along the circumferential direction of the counter electrode 21 and the reference electrode 22.

In one embodiment, referring to fig. 18, the power electrode 2 includes a counter electrode 21 and a reference electrode 22; twelve working electrodes 3 are arranged, and twelve working electrodes 3 are uniformly distributed along the circumference of the counter electrode 21 and the reference electrode 22 in two circles.

It should be noted that, in practical applications, the area of the guiding layer 4 occupies about one fifth of the whole area of the substrate 1, the guiding layer 4 is located above the substrate 1, and the substrate 1 is generally slender so as to facilitate the spreading of the liquid on the guiding layer 4.

Example two

Fig. 19 illustrates a method of manufacturing an electrochemical sensor, and referring to fig. 19, an embodiment of the present application provides a method of manufacturing an electrochemical sensor, the method including:

step 201: a substrate 1 is provided.

Step 202: the power supply electrode 2 and the plurality of working electrodes 3 are formed on the substrate 1 by a printing process and dried.

Specifically, the printing process may be screen printing, and when the power supply electrode 2 and the working electrode 3 are printed, the arrangement and positions of the power supply electrode 2 and the working electrode 3 may be set as required, and hot air drying or moisture absorption drying may be adopted during drying.

Step 203: an insulating layer 5 is formed by coating an insulating paste on the leads of the power supply electrode 2 and the plurality of working electrodes 3, and dried.

Specifically, the insulating paste may be an epoxy resin, and the insulating layer 5 functions to protect the electrodes.

Step 205: the reagent enzyme is printed on the plurality of working electrodes 3 by a printing process and dried.

Step 206: the power supply electrode 2 and the plurality of working electrodes 3 are covered with a guide layer 4.

In one embodiment, referring to fig. 20, the step of covering the conducting layer 4 on the power electrode 2 and the working electrode includes:

step 301: a guide layer 4 is formed on the substrate 1 such that the power supply electrode 2 and the working electrode 3 are covered with the guide layer 4.

Specifically, the guide layer 4 may be fixedly attached to the substrate 1 by means of adhesion.

Step 302: the guiding layer 4 is processed by an etching or shearing process.

Specifically, the guide layer 4 is etched or cut so that the shape of the guide layer 4 is the same as the shape constituted by the first region 11 and the second region 12. In this way, the guiding layer 4 can be made to better guide the liquid to spread toward a predetermined position.

In one embodiment, referring to fig. 21, the step of covering the conducting layer 4 on the power electrode 2 and the working electrode 3 includes:

step 401: the guide layer 4 is processed by a shearing process.

Specifically, the shape of the guide layer 4 is processed into the same shape as the shape constituted by the first region 11 and the second region 12.

Step 404: the processed guide layer 4 is attached to the substrate 1 so that the power supply electrode 2 and the working electrode 3 are covered with the guide layer 4.

It should be noted that, in the present specification, the embodiments are all described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments may be referred to each other.

It should also be noted that, in this document, the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be configured and operated in a specific orientation, and thus, should not be construed as limiting the present application. Moreover, relational terms such as "first" and "second" are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions or should not be construed as indicating or implying relative importance. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or terminal equipment comprising the element.

The technical solutions provided by the present application are described in detail above, and the principles and embodiments of the present application are described herein by using specific examples, which are only used to help understanding the present application, and the content of the present description should not be construed as limiting the present application. While various modifications of the illustrative embodiments and applications will be apparent to those skilled in the art based upon this disclosure, it is not necessary or necessary to exhaustively enumerate all embodiments, and all obvious variations and modifications can be resorted to, falling within the scope of the disclosure.

Claims (7)

1. An electrochemical sensor, characterized by:

comprises a substrate (1) and an electrode arranged on the substrate (1);

the electrodes comprise a power supply electrode (2) and a plurality of working electrodes (3), the surfaces of the working electrodes (3) are respectively provided with a plurality of reagent enzymes, and the reagent enzymes on the surface of each working electrode (3) are different;

wherein the power supply electrode (2) is located in a first area (11) of the substrate (1); the plurality of working electrodes (3) are located in a second region (12) of the substrate (1);

the second region (12) comprises a plurality of sub-regions (121), the plurality of sub-regions (121) are mutually independent on the substrate (1), and the plurality of working electrodes (3) are respectively positioned in different sub-regions (121);

still include guide layer (4), guide layer (4) are paper material, guide layer (4) are located the top of electrode, guide layer (4) cover first region (11) with second region (12), just one edge of guide layer (4) extends to the edge setting of base plate (1).

2. The electrochemical sensor of claim 1, wherein:

the material of the guide layer (4) comprises: filter paper, chromatography paper or blotting paper.

3. The electrochemical sensor of claim 1, wherein:

the working electrodes are positioned on one side or two sides of the power supply electrode;

alternatively, the plurality of working electrodes are arranged at even intervals along the circumferential direction of the power supply electrode.

4. The electrochemical sensor of claim 1, wherein:

the width of the guide layer in the second region is 10 μm-5 mm.

5. The electrochemical sensor of claim 1, wherein:

the power supply electrode includes: an active electrode.

6. The electrochemical sensor of claim 1, wherein:

the power supply electrode includes: a counter electrode and a reference electrode.

7. A method of manufacturing an electrochemical sensor, the method comprising:

providing a substrate;

forming a power supply electrode and a plurality of working electrodes on the substrate through a printing process, and drying;

covering the leads of the power supply electrode and the working electrodes with insulating slurry to form an insulating layer, and drying;

printing reagent enzyme on the working electrodes through a printing process, and drying;

a guiding layer covers the power supply electrode and the plurality of working electrodes.

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