Electrochemical multi-electrode coplanar array microelectrode with micro electrolytic cell and its application in micro liquid molecule detection

Abstract

The application provides a micro electrolytic cell for an electrochemical multi-electrode coplanar array type microelectrode and application thereof in micro liquid molecule detection, and specifically comprises a working electrode, a reference electrode and an auxiliary electrode; wherein multiple working electrodes share the same auxiliary electrode with a single or multiple reference electrodes, a single working electrode, a reference electrode and an auxiliary electrode constitute a detection channel, and the array type microelectrode comprises multiple detection channels and can simultaneously detect different substances. A micro electrolytic cell is arranged on the surface of the array type microelectrode, and specifically, a dam type micro electrolytic cell is constructed on the surface of the microelectrode by using PCB ink, which can be composed of one layer or multiple layers of ink. The multiple layers of ink can be multiple layers of electrolytic cells with the same diameter, or multiple layers of concentric circular electrolytic cells with gradually expanding diameters from bottom to top.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical detection, specifically relating to an electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell and its application in the detection of trace liquid molecules. Background Technology

[0002] Electrochemical sensors have garnered widespread attention due to their fast detection speed, accurate values, and suitability for on-site emergency detection. To date, the development of electrochemical sensors has evolved from pursuing high sensitivity to highly integrated and portable detection. However, existing electrochemical sensors still suffer from drawbacks such as difficulty in fabrication, application challenges, and poor stability and repeatability. Furthermore, the complex fabrication process of electrochemical sensors prevents their integration into microchip-based integrated sensors, thus limiting their application in a wider range of fields and scenarios. Based on these factors, the development of micro-integrated electrochemical sensors is therefore essential.

[0003] Point-of-care electrochemical sensors are characterized by speed, convenience, and cost-effectiveness. Specifically, they provide immediate detection results, reduce the cost per test, and meet the requirement of obtaining accurate test results in the shortest possible time. As a result, they are gradually being widely used in fields such as biomedicine and environmental monitoring.

[0004] Currently, the core detection elements of point-of-care electrochemical sensors mostly use detection cards and detection strips as consumables. Due to the technical requirements of multi-parameter electrochemical detection, the processing technology of such detection elements is complex and cumbersome, and the cost is high, which is not conducive to mass production. The process is difficult and the application range is also limited.

[0005] To address the above issues, this patent provides an electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell, which simplifies the processing technology, reduces production costs, facilitates the mass production of similar products, and can be applied to the detection of trace liquid molecules such as blood and urine. Summary of the Invention

[0006] In view of this, the present invention provides an electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell and its application in the detection of trace liquid molecules.

[0007] The purpose of this invention is to provide an electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell. The array microelectrode includes multiple coplanar microelectrodes, each of which specifically includes a working electrode, a reference electrode, and an auxiliary electrode. The multiple working electrodes share the same auxiliary electrode with one or more reference electrodes. A single working electrode, reference electrode, and auxiliary electrode constitute a detection pathway. The array microelectrode includes multiple detection pathways, enabling simultaneous detection of different substances.

[0008] Furthermore, the distance between the working electrode and the auxiliary electrode is 0.1–1.5 mm; the distance between the reference electrode and the auxiliary electrode is 0.1–1.5 mm.

[0009] Furthermore, the working electrode, auxiliary electrode, and reference electrode in the array microelectrode are regular shapes with consistent forms, including square, circular, and elliptical shapes.

[0010] A micro-electrolytic cell is set up in the array-type microelectrode region, specifically using PCB ink to construct the dam. A multi-layered structure can be built through multi-layer ink coating. The micro-electrolytic cell dam is higher than the electrode plane, which helps protect the surfaces of the working electrode, reference electrode, and auxiliary electrode from external scratches. The micro-electrolytic cell, with its size progressively increasing from the electrode surface, facilitates the quantitative addition of modification solutions to the working electrode, including enzymes, solid electrolytes, and gel electrolytes.

[0011] The micro-electrolysis cell structure can form a vortex structure in the micro-region, which is conducive to the effective "enrichment" of the molecules to be detected in the liquid. The fixed area of ​​the micro-electrolysis cell is beneficial for the quantitative analysis of trace liquid molecules.

[0012] Furthermore, a micro-electrolysis cell is provided on the surface of the array-type microelectrode, specifically by using PCB ink to construct a dam-type micro-electrolysis cell on the surface of the microelectrode.

[0013] Furthermore, the micro electrolytic cell is composed of one or more layers of ink. The multilayer ink can be multiple electrolytic cells of the same size, or it can be a multilayer concentric electrolytic cell with the size gradually increasing from bottom to top.

[0014] Furthermore, the area of ​​the micro-electrolytic cells constructed on the same type of electrode surface is fixed and slightly higher than the electrode plane. The total thickness of the ink dams in the micro-electrolytic cells is 10–1500 μm.

[0015] The electrochemical multi-electrode coplanar array microelectrode with micro-electrolysis cell provided by the present invention further includes an electrode substrate, a microfluidic cell, and electrode pins. The array microelectrode, the microfluidic cell, and the electrode pins are all disposed on the front side of the electrode substrate. The array microelectrode is disposed inside the microfluidic cell. The array microelectrode and the electrode pins are connected by metal lines on the surface of the electrode substrate. The number of electrode pins is the same as the number of array microelectrodes.

[0016] Furthermore, the electrode pins are uniformly spaced and their shapes include rectangular electrode strips and circular electrode sheets.

[0017] This invention places arrayed microelectrodes and electrode pins on the same plane. The circuit connecting the microelectrodes and electrode pins can be set as a metal circuit on the surface of the electrode substrate, without the need for buried wires inside the substrate. This expands the range of electrode substrate materials and significantly reduces processing costs and process difficulty.

[0018] Furthermore, the electrode substrate can be ceramic, polymer material, or silicon-based.

[0019] As attached Figure 1 The figure shows a schematic diagram of an electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell provided by the present invention. As shown in the figure, an array of microelectrodes and electrode leads are coplanarly arranged on the front side of the electrode substrate. The array microelectrode consists of a working electrode, an auxiliary electrode, and a reference electrode, specifically including seven working electrodes, one auxiliary electrode, and seven reference electrodes, wherein the working electrode and the reference electrode are respectively disposed on both sides of the auxiliary electrode. The fifteen microelectrodes and electrode leads are connected by metal lines on the surface of the electrode substrate, forming seven detection pathways, which can specifically detect seven different substances.

[0020] As attached Figure 2 The figure shows a schematic diagram of a microfluidic cell for an electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell provided by the present invention. As shown in the figure, a microfluidic system is set in the microfluidic cell area marked by the dashed box, so that the liquid to be tested flows through all the microelectrodes in sequence.

[0021] As attached Figure 3 The figure shows a front view of the electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell in Example 5. As can be seen, a circular microfluidic cell is disposed on the upper side of the electrode substrate. The microfluidic cell contains an array of microelectrodes, including four working electrodes, one auxiliary electrode, and one reference electrode, forming an array unit. Specifically, the working electrodes are symmetrically distributed at the four corners of the reference electrode, which has a missing corner, and a circular auxiliary electrode is disposed on the outer side. The four working electrodes in the array microelectrode share the auxiliary electrode and the reference electrode, forming four detection pathways that can specifically detect four different substances.

[0022] As attached Figure 4 The figure shows a schematic diagram of the back side of the electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell in Example 5. As can be seen from the figure, there are six long rectangular electrode pins on the lower side of the back side of the electrode substrate, the same number as the microelectrodes on the front side. The array microelectrodes and the electrode pins are connected one by one through the metal lines on the back side of the electrode substrate.

[0023] As attached Figure 5 The image shows a schematic cross-sectional view of a microelectrolysis cell on the surface of an array of microelectrodes. Figure 5 A involves modifying the surface of an array of microelectrodes with a single layer of enclosing dams to form a single-layer microelectrolysis cell. Figure 5 B involves modifying the surface of an array of microelectrodes with multiple layers of uniformly sized, multi-level micro-electrolytes. Figure 5C is a concentric circular microelectrolysis cell with multiple layers of gradually increasing diameter from bottom to top, modified on the surface of an array of microelectrodes.

[0024] Another objective of this invention is to provide an application of an electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell in the detection of trace liquid molecules, specifically including the detection of small molecules in blood and urine.

[0025] As attached Figure 6 The figures show (a) a schematic diagram of the flow rate profile of the test liquid within the micro-electrode with a micro-electrolysis cell, (b) a schematic diagram of the concentration distribution of the test liquid within the micro-electrolysis cell, (c) a magnified view of a portion of the working electrode surface, and (d) a schematic diagram of copper ion deposition eddies, all provided by this invention, in the detection of trace liquid molecules. As can be seen from the figures, with a dam height of 1.0 mm in the micro-electrolysis cell and a copper ion concentration of 6 x 10⁻⁶ in the serum sample buffer, [the following data is presented]. -6 Under the conditions of mol / L and an initial solution velocity of 0.007 m / s, where L is the thickness of the diffusion layer, a significant vortex structure is formed near the electrode in the micro-electrolysis cell constructed on the surface of the microelectrode, which interferes with the deposition of copper ions in the test solution, thereby achieving effective enrichment of copper ions on the surface of the working electrode.

[0026] As attached Figure 7 The figure shows the relationship between the detection electrical signal and the residence time for copper ion detection using the electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell provided by this invention. It can be seen from the figure that the longer the residence time of the test liquid on the surface of the working electrode, the better for the detection of the electrical signal.

[0027] As attached Figure 8 The figures show (a) the relationship between the electrolytic cell height and the diffusion layer thickness, and (b) the relationship between the electrolytic cell height and the electrode sensing signal for copper ion detection using the electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell provided by this invention. It can be seen from the figures that the copper ion concentration in the serum sample solution is 6 x 10⁻⁶. -6 At a flow rate of 0.007 m / s and a concentration of mol / L, the electrochemical sensing signal was enhanced as the height of the dam in the micro-electrolytic cell increased from 0.6 mm to 1.4 mm.

[0028] As attached Figure 9 The figures show (a) the relationship between liquid flow rate and electrolytic cell height, and (b) the relationship between liquid flow rate and electrode sensing signal for copper ion detection using the electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell provided by this invention. It can be seen from the figures that the copper ion concentration in the serum sample solution is 6 x 10⁻⁶. -6With a mol / L concentration and a micro-electrolytic cell dam height of 1.0 mm, as the sample flow velocity increased from 0.003 m / s to 0.011 m / s, the slower the liquid flow velocity, the stronger the electrochemical sensing signal.

[0029] In summary, constructing a micro-electrolytic cell with ink dams on the surface of the working electrode is beneficial for the detection of liquid molecules by array-type microelectrodes.

[0030] The present invention can set up a microfluidic system in the microfluidic cell area, so that the liquid to be tested flows through all the microelectrodes in sequence through the inlet and then is discharged through the outlet, forming a multi-electrode highly integrated sensor chip that can simultaneously detect multiple material indicators.

[0031] Integrating multiple electrodes on the electrode substrate surface in an array is beneficial for planning microfluidic routes and detection circuits, and for reducing and fixing the electrode spacing, resulting in more accurate and stable detection results.

[0032] The beneficial effects of this invention are:

[0033] (1) The present invention sets the array microelectrode and the electrode pin connected to it on the same electrode substrate surface, avoiding the need to embed wires in the electrode substrate. Only metal lines need to be processed on the substrate surface, which greatly reduces the processing cost and process difficulty, expands the range of electrode substrates to be selected, and is suitable for special environments such as high temperature and high pressure.

[0034] (2) In this invention, a multi-layered micro-electrolysis cell is constructed on the surface of an array of microelectrodes using ink. The ink dam, which is slightly higher than the working electrode plane, helps to form a vortex structure in the micro-regions on the electrode surface when detecting the liquid to be tested. This allows for the effective enrichment of the liquid molecules, enhances the detection signal, and increases the detection sensitivity and accuracy. At the same time, it is easy to protect the array of microelectrodes from external contamination and scratches. The fixed area of ​​the micro-electrolysis cell facilitates the quantitative analysis of trace liquid molecules. The multi-layered micro-electrolysis cell structure, with its size gradually increasing from bottom to top, facilitates the quantitative addition of the modification solution to the working electrode, including enzymes, solid electrolytes, gel electrolytes, etc.

[0035] (3) The present invention integrates the array microelectrodes of the three-electrode system in the same area of ​​the electrode substrate and fixes and shortens the distance of the three-electrode system, which is conducive to stable signal transmission and improves the sensitivity and stability of the microelectrodes. At the same time, the array microelectrode design is also easy to process and is conducive to the design and planning of microfluidic systems and the control of the injection liquid flow rate. Attached Figure Description

[0036] The invention will be further illustrated with reference to the accompanying drawings, but the embodiments in the drawings do not constitute any limitation on the invention. For those skilled in the art, other drawings can be obtained based on the following drawings without any creative effort.

[0037] Figure 1 This is a schematic diagram of an electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell provided by the present invention;

[0038] Figure 2 This is a schematic diagram of a microfluidic cell with a microelectrode coplanar array of electrochemical multi-electrode microelectrodes provided by the present invention;

[0039] Figure 3 This is a front view of the electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell in Example 5;

[0040] Figure 4 This is a schematic diagram of the back side of the electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell in Example 5;

[0041] Figure 5 This is a schematic diagram of a cross-section of a microelectrolysis cell on the surface of an array of microelectrodes;

[0042] Figure 6 (a) Schematic diagram of the flow velocity profile of the liquid to be tested in a micro-electrolysis cell; (b) Schematic diagram of the concentration distribution of the liquid to be tested in a micro-electrolysis cell; (c) Schematic diagram of a partial magnified view of the working electrode surface; (d) Schematic diagram of the copper ion deposition eddy current.

[0043] Figure 7 This is a graph showing the relationship between the detection electrical signal and residence time of copper ions;

[0044] Figure 8 (a) The relationship between the height of the electrolytic cell and the thickness of the diffusion layer, and (b) The relationship between the height of the electrolytic cell and the electrode sensing detection signal;

[0045] Figure 9 (a) The relationship between liquid flow rate and electrolytic cell height, and (b) The relationship between liquid flow rate and electrode sensing detection signal.

[0046] Legend:

[0047] Figure 1 In the diagram, A is the working electrode 1; B is the working electrode 2; C is the working electrode 3; D is the working electrode 4; E is the working electrode 5; F is the working electrode 6; G is the working electrode 7; H is the reference electrode 1; I is the reference electrode 2; J is the reference electrode 3; K is the reference electrode 4; L is the reference electrode 5; M is the reference electrode 6; N is the reference electrode 7; and O is the auxiliary electrode.

[0048] Figure 2In the diagram, 1. Electrode pin 1; 2. Electrode pin 2; 3. Electrode pin 3; 4. Electrode pin 4; 5. Electrode pin 5; 6. Electrode pin 6; 7. Electrode pin 7; 8. Electrode pin 8; 9. Electrode pin 9; 10. Electrode pin 10; 11. Electrode pin 11; 12. Electrode pin 12; 13. Electrode pin 13; 14. Electrode pin 14; 15. Electrode pin 15.

[0049] Figure 3 In the diagram, A is the working electrode 1; B is the working electrode 2; C is the working electrode 3; D is the working electrode 4; E is the reference electrode; and F is the auxiliary electrode.

[0050] Figure 4 In the diagram, 1 is electrode pin 1; 2 is electrode pin 2; 3 is electrode pin 3; 4 is electrode pin 4; 5 is electrode pin 5; and 6 is electrode pin 6. Detailed Implementation

[0051] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail with reference to the following specific embodiments and the accompanying drawings.

[0052] Specific embodiments of the present invention include:

[0053] Example 1

[0054] An electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell integrates the working electrode, reference electrode, and auxiliary electrode on a microfluidic region on the same electrode substrate surface, and installs a microfluidic module including a sample inlet on the left and a sample outlet on the right to control the flow of the test solution through the three-electrode system. A single-layer micro-electrolytic cell is constructed on the microelectrode surface using a PCB, with the dam height of the micro-electrolytic cell set to 1.0 mm. The cross-section of the electrolytic cell shows the attached... Figure 5 A. With a copper ion concentration of 6 x 10⁻⁶ - 6 A serum solution of mol / L was used as the test liquid. The initial velocity of the solution was set to 0.007 m / s. The fluid state of the serum solution flowing through the working electrode was observed, and the electrical signal of copper ions detected by the array microelectrode was recorded to obtain the attached... Figure 6 and attached Figure 7 .

[0055] Example 2

[0056] An electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell integrates the working electrode, reference electrode, and auxiliary electrode on a microfluidic region on the same electrode substrate surface, and installs a microfluidic module, including a sample inlet on the left and a sample outlet on the right, to control the flow of the test solution through the three-electrode system. A multi-layered circular micro-electrolytic cell of the same diameter is constructed on the microelectrode surface using a PCB, and the total height of the dam surrounding the electrolytic cell is adjusted. The cross-section of the electrolytic cell shows the attached...Figure 5 B. With a copper ion concentration of 6 x 10⁻⁶ - 6 A serum solution of mol / L was used as the test liquid. The initial velocity of the solution was set to 0.007 m / s. Under the same conditions, copper ion detection was performed using an array of microelectrodes with different dam heights in a microelectrolytic cell. The dam height of the microelectrolytic cell increased from 0.6 mm to 1.4 mm. The electrical signals of copper ions detected by the array of microelectrodes were recorded, and the results were obtained. Figure 8 .

[0057] Example 3

[0058] An electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell integrates the working electrode, reference electrode, and auxiliary electrode on a microfluidic region on the same electrode substrate surface, and installs a microfluidic module, including a sample inlet on the left and a sample outlet on the right, to control the flow of the test solution through the three-electrode system. A multi-layered concentric circular micro-electrolytic cell with gradually increasing diameter from bottom to top is constructed on the microelectrode surface using a PCB. The cross-section of the electrolytic cell shows the attached... Figure 5 C. The total height of the dam surrounding the micro-electrolyte is set to 1.0 mm. The copper ion concentration is 6 x 10⁻⁶. -6 A serum solution of mol / L was used as the test liquid. The initial velocity of the solution was adjusted from 0.003 m / s to 0.011 m / s. The electrical signal of copper ions was recorded and detected by an array of microelectrodes. The initial fluid velocity was obtained by... Figure 9 .

[0059] Example 4

[0060] An electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell, as shown in the attached figure. Figure 1 As shown, an array of microelectrodes and electrode leads are coplanarly arranged on the front side of the electrode substrate. The array of microelectrodes consists of working electrodes, auxiliary electrodes, and reference electrodes, specifically including seven working electrodes, one auxiliary electrode, and seven reference electrodes. The working electrodes and reference electrodes are respectively disposed on both sides of the auxiliary electrode. The auxiliary electrode is a single elongated rectangular electrode. The seven working electrodes are rectangular electrodes of the same shape and size, distributed on the upper side of the auxiliary electrode, and the seven reference electrodes are rectangular electrodes of the same shape and size, distributed on the lower side of the auxiliary electrode.

[0061] As attached Figure 2 As shown, a microfluidic system is set up in the microfluidic area marked by the dashed box, so that the liquid to be tested flows through all the microelectrodes in sequence.

[0062] The surface of the arrayed microelectrodes is constructed with PCB ink to form dams, creating micro-electrolytic cells. The area of ​​the micro-electrolytic cells is fixed and slightly higher than the electrode plane, as shown in the attached figure. Figure 5 As shown.

[0063] Fifteen microelectrodes and electrode pins are connected by metal lines on the surface of the electrode substrate, forming seven detection pathways that can specifically detect seven different substances.

[0064] In this embodiment, a ceramic substrate is selected as the electrode substrate. In the array-type microelectrode, the working electrode, reference electrode, and auxiliary electrode are respectively connected to the corresponding elongated rectangular electrode pins on the same plane. The seven working electrodes are rectangular microelectrodes with the same shape and area, the seven reference electrodes are rectangular microelectrodes with the same shape and area, and the auxiliary electrode is an elongated microelectrode. The fifteen microelectrodes are connected to the uniformly distributed elongated electrode pins below the substrate through metal lines processed on the surface of the ceramic substrate. The fifteen lines do not intersect or contact each other. The specific details are shown in the table below:

[0065] Table 1. Statistical Table of Conductivity between Arrayed Microelectrodes and Electrode Pins

[0066]

[0067]

[0068] A micro-electrolysis cell is fabricated using PCB ink in the arrayed microelectrode area on the front side of the electrode substrate. The test solution flows sequentially across the surface of the arrayed microelectrodes, and the changes in the electrical signals of the three electrodes are read through the electrode pins to achieve the detection of specific target substances. A set of three electrodes can constitute a detection pathway, as detailed in the table below:

[0069] Table 2. Statistical Table of Detection Paths for Microelectrode Integrated Sensing Chips

[0070] Detection path Working electrode Reference electrode Auxiliary electrode 1 A H O 2 B 1 O 3 C J O 4 D K O 5 E L O 6 F M O 7 G N O

[0071] Example 5

[0072] An electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell, as shown in the attached figure. Figure 3 As shown, a circular microfluidic cell is positioned on the upper side of the electrode substrate. Within the microfluidic cell, an array of microelectrodes is distributed, including four working electrodes, one auxiliary electrode, and one reference electrode, forming an array unit. Specifically, with the reference electrode (a rectangular shape with missing corners) at the center, the working electrodes are symmetrically distributed at the four corners, and a ring-shaped auxiliary electrode is positioned on the outer side (see attached diagram). Figure 3 (Middle black circular electrode).

[0073] A microfluidic system is set up in the outer circular microfluidic region so that the liquid to be tested flows through all the microelectrodes in sequence.

[0074] As attached Figure 4As shown, a long rectangular electrode pin is provided on the lower side of the back of the electrode substrate. The number of pins is six, which is the same as the number of microelectrodes on the front. The array of microelectrodes and the electrode pins are connected one by one through the metal lines on the back of the electrode substrate.

[0075] The surface of the arrayed microelectrodes is constructed with PCB ink to form dams, creating micro-electrolytic cells. The area of ​​the micro-electrolytic cells is fixed and slightly higher than the electrode plane, as shown in the attached figure. Figure 5 As shown.

[0076] In an array-type microelectrode, four working electrodes share an auxiliary electrode and a reference electrode, forming four detection pathways that can specifically detect four different substances.

[0077] In the array-type microelectrode, the working electrodes A, B, C, and D are connected to electrode pins 1, 6, 2, and 5 respectively, the reference electrode E is connected to electrode pin 3, and the auxiliary electrode F is connected to electrode pin 4. The internal circuitry of the electrode substrate is not in contact with each other, as detailed in the table below:

[0078] Table 3. Statistical Table of Conductivity between Arrayed Microelectrodes and Electrode Pins

[0079] Serial number Microelectrode Electrode contact Electrode type 1 A 1 Working electrode 1 2 B 6 Working electrode 2 3 C 2 Working electrode 3 4 D 5 Working electrode 4 5 E 3 Reference electrode 6 F 4 Auxiliary electrode

[0080] A microfluidic system is set in the microfluidic cell area on the front of the sensor chip, allowing the test solution to flow sequentially over the surface of an array of microelectrodes. Changes in the electrical signals of the three electrodes are read through the electrode pins on the back of the sensor chip, enabling the detection of specific target substances. A set of three electrodes can constitute a detection pathway, as detailed in the table below:

[0081] Table 4. Statistical Table of Detection Paths for Microelectrode Integrated Sensing Chips

[0082] Detection path Working electrode Reference electrode Auxiliary electrode 1 A E F 2 B E F 3 C E F 4 D E F

[0083] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0084] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can be appropriately combined to form other embodiments that can be understood by those skilled in the art. Technical details not described in detail in this invention can all be implemented using any existing technology in the art. In particular, all technical features not described in detail in this invention can be implemented using any existing technology.

Claims

1. An electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell, characterized in that, The array-type microelectrode includes multiple coplanar microelectrodes, each microelectrode specifically including a working electrode, a reference electrode, and an auxiliary electrode; wherein multiple working electrodes share the same auxiliary electrode with one or more reference electrodes, and a single working electrode, the reference electrode, and the auxiliary electrode constitute a detection pathway; the array-type microelectrode includes multiple detection pathways, enabling simultaneous detection of different substances; The surface of the array-type microelectrode is provided with a micro-electrolysis cell; The micro electrolytic cell is composed of multiple layers of ink, which are multi-layered concentric circular electrolytic cells with a gradually increasing diameter from bottom to top. The multi-layered concentric circular electrolytic cell can form a vortex structure; The micro-electrolytic cells constructed on the same type of electrode surface have a fixed area, slightly higher than the electrode plane, and the total thickness of the dam surrounding the micro-electrolytic cells is 10 to 1500 μm.

2. The electrochemical multi-electrode coplanar array microelectrode with a micro-electrolysis cell according to claim 1, characterized in that, In the array-type microelectrode, the distance between the working electrode and the auxiliary electrode is 0.1–1.5 mm; the distance between the reference electrode and the auxiliary electrode is 0.1–1.5 mm.

3. A coplanar array microelectrode with a micro-electrolytic cell according to claim 1 or 2, characterized in that, The working electrode, the auxiliary electrode, and the reference electrode in the array microelectrode are all regular shapes with the same shape, including square, circular, and elliptical.

4. The electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell according to claim 3, characterized in that, The surface of the microelectrode is constructed with PCB ink to form a dam-type microelectrolytic cell.

5. An electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell as described in any one of claims 1-3, characterized in that, The array-type microelectrode further includes an electrode substrate, a microfluidic cell, and electrode pins. The array-type microelectrode, the microfluidic cell, and the electrode pins are all disposed on the front side of the electrode substrate. The array-type microelectrode is disposed inside the microfluidic cell. The array-type microelectrode and the electrode pins are connected by metal lines on the surface of the electrode substrate. The number of electrode pins is the same as the number of array-type microelectrodes.

6. The electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell according to claim 5, characterized in that, The electrode pins are uniformly spaced and have shapes including rectangular electrode strips and circular electrode sheets.

7. An application of the electrochemical multi-electrode coplanar array microelectrode with a micro-electrolytic cell as described in claim 5 in the detection of trace liquid molecules, including the detection of small molecules in blood and urine.

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