Hollowed-out ion selective electrode and application thereof

Abstract

The invention provides a hollow ion selective electrode and application thereof, a front conductive circuit (2) and an electrode loading area (1) are arranged on the front surface of a substrate, the front conductive circuit (2) is provided with a via hole (24), and the electrode loading area (1) comprises an electrode detection layer and a first hollow hole (13) penetrating through the substrate; the back surface of the substrate is provided with a first hollow hole (13) and a back surface conductive circuit (4), the back surface conductive circuit (4) is provided with a via hole (24), and the front surface conductive circuit (2) and the back surface conductive circuit (4) are connected with each other through the via hole (24); an insulating double-sided adhesive tape (41), a selective electrode patch (42) and a conductive adhesive tape (43) are arranged on the back surface of the substrate, the selective electrode patch (42) is tightly attached to the substrate through the insulating double-sided adhesive tape (41), the conductive adhesive tape (43) is arranged above the selective electrode patch (42), and the selective electrode patch (42) is fixed on the back surface of the substrate and is in contact conduction with the back surface conductive circuit (4).

Description

Technical Field

[0001] The invention belongs to the field of electrochemical sensors and relates to a hollow ion selective electrode and applications thereof. Background Art

[0002] Electrodes are the most important sensitive components in electrochemical sensors. Sensors generally require two or more electrodes, and three-electrode systems are currently the most widely used. These three electrodes consist of a working electrode, a reference electrode, and a counter electrode. However, the three electrodes in a traditional three-electrode system are not integrated on a single plane, and the electrodes are spaced far apart. During electrochemical testing, concentration polarization is prone to occur between the working and counter electrodes, affecting test accuracy. Furthermore, the large size of traditional three-electrode systems makes them inconvenient for the design and processing of microsensors, limiting their application.

[0003] Patent CN201920553197.X discloses a portable three-electrode structure, which specifically integrates the working electrode, counter electrode and reference electrode on the same plane, greatly reducing the size of the three electrodes and facilitating the design and processing of microsensors.

[0004] However, the working electrode modification layer of the above-mentioned electrode is fixed and cannot be replaced according to the detection target, which may cause waste during use and cause some inconvenience in the specific use of the electrode. At the same time, different modification layers are modified on the surfaces of the three electrodes on the basis of the coplanarity of the three electrodes, which also brings difficulties to the electrode repair and processing. The electrode processing cost is relatively high and there are also some inconveniences in use.

[0005] Patent CN218938192U discloses a graphene three-electrode coplanar standard electrode, which specifically involves digging a hole on the electrode substrate to form an electrode modification hole, and providing an electrode modification ring structure concentrically around the electrode modification hole on the back side. An electrode modification layer is installed at the position of the electrode modification ring. The electrode modification layer conducts electricity and transmits signals by contacting the electrode modification ring, and the electrode modification layer is fixed by glue sealing.

[0006] However, although the above-mentioned electrode proposes to separate the key working electrode modification layer and perform subsequent installation and fixation according to the requirements of the detection molecules, there are still tiny gaps in the later installed structure. When the detection liquid droplet is added to the electrode modification hole position and contacts the electrode modification layer to react, the tiny gap between the electrode modification layer and the back of the substrate causes the electrode detection area to change and cannot be fixed, thereby greatly affecting the stability and accuracy of the detection data; in order to transmit the electrical signal generated by the electrode patch, a ring-shaped conductive structure is set in the contact area between the electrode patch and the electrode substrate, and the electrical signal is transmitted to the electrode pin by the ring structure. The effect of this ring structure in conducting electricity and transmitting signals is also not good, which affects the sensitivity of the electrode.

[0007] In order to further overcome the above problems, this patent aims to provide a hollow ion-selective electrode, which can be freely assembled with selective electrode patches according to the requirements of the detection object, and fix the area of ​​the electrode detection area, so that its detection accuracy and stability can reach the performance level of a normal three-electrode coplanar electrode. While ensuring the electrode detection performance, it is more flexible, reduces processing and use costs, and opens up broader application prospects for microelectrodes. Summary of the Invention

[0008] In summary, the present invention provides a hollow ion-selective electrode and applications thereof.

[0009] The present invention aims to provide a hollow ion-selective electrode, comprising an electrode substrate, characterized in that a front conductive circuit (2) and an electrode loading area (1) are provided on the front surface of the substrate, a conductive hole (24) is provided on the front conductive circuit (2), and the electrode loading area (1) includes an electrode detection layer and a first hollow hole (13) penetrating the substrate; the first hollow hole (13) and a back conductive circuit (4) are coplanarly provided on the back surface of the substrate, a conductive hole (24) is provided on the back conductive circuit (4), and the front conductive circuit (2) and the back conductive circuit (4) are connected through the conductive hole (24). Interconnection; an insulating double-sided tape (41), a selective electrode patch (42) and a conductive tape (43) are also provided on the back of the substrate. The selective electrode patch (42) is tightly attached to the substrate through the insulating double-sided tape (41) and completely covers the position of the first hollow hole (13). The insulating double-sided tape (41) has a second hollow hole at a position corresponding to the first hollow hole (13). The conductive tape (43) is provided above the selective electrode patch (42), fixes the selective electrode patch (42) to the back of the substrate, and contacts and conducts with the back conductive circuit (4).

[0010] The electrode detection layer comprises a first electrode layer (11) and a second electrode layer (12) which are arranged on the same plane and are not interconnected. A first hollow hole (13) is arranged adjacent to the first electrode layer (11) and the second electrode layer (12). The first electrode layer (11) and the second electrode layer (12) are respectively connected to the front conductive circuit (2).

[0011] As attached Figure 1 The figure shows a front view of a hollow ion selective electrode.

[0012] The positions of the first electrode layer (11), the second electrode layer (12), and the first hollow hole (13) can refer to the conventional three-electrode coplanar electrode surface three-electrode position arrangement, and the distance between the three electrodes is shortened as much as possible to eliminate concentration polarization and improve electrode sensitivity. In the embodiment of the present invention, the first electrode layer (11) is partially annular, and the first hollow hole (13) is wrapped inside the ring. The second electrode layer (12) is located on the other side of the missing ring shape, wherein the first electrode layer (11) corresponds to the counter electrode, the second electrode layer (12) corresponds to the reference electrode, and the first hollow hole (13) corresponds to the working electrode. Such an arrangement greatly reduces the distance between the working electrode and the counter electrode, promotes the miniaturization of the coplanar electrode and improves the sensitivity. The electrode position arrangement of the present invention can also symmetrically arrange the first electrode layer (11) and the second electrode layer (12) on both sides of the first hollow hole (13), and the three-electrode position arrangement can be adjusted according to actual needs.

[0013] The first hollow hole (13) may be in a regular shape including a circle and a rectangle.

[0014] The front conductive circuit (2) comprises a first circuit (21), a second circuit (22) and a third circuit (23) which are not connected to each other, the first circuit (21) being connected to the first electrode layer (11), the second circuit (22) being connected to the second electrode layer (12), and the third circuit (23) being arranged outside the first hollow hole (13).

[0015] One or more vias (24) are provided on the third circuit (23). The vias (24) are also located on the back conductive circuit (4) on the back side of the substrate and are interconnected with the third circuit (23) through the vias (24).

[0016] The conductive holes and the conductive circuits are generally filled with a metal layer, which can connect the conductive circuit metal layers on the front and back of the substrate. The number of conductive holes is set to one or more, usually three, to ensure that the front and back of the substrate are connected and the electrical signal transmission is normal.

[0017] As attached Figure 2 The back side of the hollow ion selective electrode is shown in the figure. Figure 1 .

[0018] In the embodiment of the present invention, the third line (23) of the electrode is not connected to the first hollow hole (13), that is, the third line (23) on the front side of the electrode is not connected to the working electrode position, but is connected to the back conductive line (4) on the back side of the electrode base through the conductive hole (24) provided in the third line (23), and then connected to the electrode sheet subsequently loaded at the position of the first hollow hole (13) and transmits the electrical signal. This not only reduces the volume of the electrode and makes the arrangement of the lines on the electrode surface more concise, but also makes the transmission of the electrical signal smoother. It is also in line with the design concept of the present invention of loading the working electrode separately as the electrode sheet, avoiding the disadvantage that the loading electrode sheet affects the transmission of the electrical signal due to poor contact and other reasons.

[0019] Electrode pins are also provided on the front side of the substrate, including a first pin (31), a second pin (32) and a third pin (33) that are coplanar and equidistant, and are respectively connected to the first circuit (21), the second circuit (22) and the third circuit (23).

[0020] The above three electrode pins are arranged in parallel and equidistantly according to the conventional three-electrode coplanar electrode, and the entire electrode size is set to match the USB size. The metal area size and distance of the three pins can also be adjusted as needed to facilitate the transmission of electrical signals.

[0021] Furthermore, the surfaces of the front conductive circuit (2), the electrode pins, the electrode detection layer and the back conductive circuit (4) are modified with a metal layer as a base metal, and the metal type includes silver.

[0022] Furthermore, the first electrode layer (11) is provided with a modification layer on the surface of the base metal, and the material of the modification layer includes carbon.

[0023] Furthermore, a modification layer is provided on the surface of the second electrode layer (12), and the modification layer includes a silver-silver chloride layer.

[0024] The insulating double-sided tape (41) completely covers the first hollow hole (13), and a second hollow hole is provided at a position corresponding to the first hollow hole (13), the shape of which is concentric with the first hollow hole (13), and the size of which is consistent with the size of the first hollow hole (13).

[0025] The conductive tape (43) completely covers the area where the selective electrode patch (42) and the conducting hole (24) are located.

[0026] As attached Figure 3 and attached Figure 4 As shown, they are schematic diagrams of the back of the hollow ion selective electrode Figure 2 And the back Figure 3 , and attached Figure 5 Schematic diagram of the side structure of a hollow ion-selective electrode.

[0027] Conventional three-electrode coplanar electrodes require modification of different metals or modified layers in the working electrode, counter electrode and reference electrode areas respectively, but this is difficult to achieve in actual processing. The different orders and processes of the three-electrode processing may affect the processing of other electrodes, especially for the working electrode modified with the core detection layer. The process effect may be affected by the other two electrodes or more cumbersome processes may be required to avoid influencing factors. This patent separates the working electrode into a separate component, and the electrode patch can be processed or selected separately. The process is simpler and more convenient, and more types of modification processing can be performed. More targets can be detected, and more targeted selections can be made according to different targets, which greatly expands the electrode detection range and detection methods.

[0028] In order to tightly fix the electrode patch on the back of the substrate, the present invention designs a multi-layer structure, which includes an insulating double-sided tape, an electrode patch and a conductive tape. The insulating double-sided tape is attached to the back of the substrate, and a hole identical to the first hollow hole on the substrate is opened at the same position. After tearing off the upper backing paper on the other side, the electrode patch can be pasted and fixed. Because the double-sided tape is insulating, it does not affect the reaction and signal transmission generated on the electrode patch. Subsequently, the conductive tape is used to cover the electrode patch, and the electrode patch is fixed to the back of the substrate for a second time and connected to the back conductive circuit, thereby realizing the transmission of electrical signals from the electrode patch to the conductive tape, the back conductive circuit and the through hole to the third circuit and the third pin on the front.

[0029] The electrode patch is fixed on the back of the substrate. When the hollow electrode is used, the test liquid is added to the first hollow hole on the front. That is, the part of the electrode patch corresponding to the first hollow hole is the electrode detection area, and the electrochemical reaction area is also calculated based on this. However, when the electrode patch is in direct contact with the back of the substrate, it is impossible for it to fit completely tightly. There will always be tiny gaps between the materials. The test liquid may overflow from these tiny gaps, which will cause the area of ​​the electrode detection area to change, affecting the electrode detection results.

[0030] The metal part can be appropriately increased in the contact area between the conductive circuit and the conductive tape on the back side, so as to maximize the contact area between the conductive circuit and the conductive tape, thereby increasing the conductive area, making the conductive effect better and the electrical signal transmission effect better.

[0031] The present invention uses double-sided tape to fix the electrode patch to the greatest extent, fill the gaps, and minimize the tiny gaps generated by the electrode patch and the back substrate surface, thereby avoiding changes in the area of ​​the electrode detection area and the inability to fix it, which greatly affects the stability and accuracy of the detection data. The subsequent secondary fixation with conductive tape further prevents the electrode patch from being moved by external forces, covers and protects the electrode patch, and at the same time expands the contact area between the conductive tape and the electrode patch, and the contact area between the conductive tape and the back conductive circuit as much as possible, thereby connecting the electrode patch to the back conductive circuit, facilitating signal transmission, and achieving excellent results, making the electrode performance more sensitive and stable.

[0032] The selective electrode patch (42) can be made of carbon and metal, and the metal material includes gold, silver, platinum, bismuth, chromium, copper, and nickel.

[0033] The side of the selective electrode patch (42) in contact with the back of the substrate can be modified with an ion selective modification layer. The specific material of the ion selective modification layer can be arbitrarily changed according to detection requirements, including metal film, enzyme, and porous metal.

[0034] The electrode patch material can be selected from carbon, gold, silver, platinum, bismuth, chromium, copper, etc., and different types of metal ions can be detected according to the different electrode patch materials. A metal sheet can also be used as a substrate and the metal can be modified on its surface. A modified layer is set on the surface of the electrode patch, such as active enzymes or nanoporous gold, nanoporous silver or other ion-selective substances, which can selectively detect specific biochemical molecules and be used for the detection of specific substances such as biochemical molecules and heavy metals. That is, a specific electrode patch can be selected according to the target detection object and assembled into an ion-selective electrode that can detect the target detection object.

[0035] Another object of the present invention is to provide an application of a hollow ion-selective electrode in biochemical molecule detection.

[0036] As attached Figure 6 As shown, the electrochemical curve of the hollow ion selective electrode using the SWASV method to detect metal tellurium, where Figure 6 (a) is the SWASV curve, Figure 6 (b) is a linear fitting plot. As can be seen from the figure, the curve obtained for detecting tellurium ions using a gold electrode as the electrode patch is well-shaped, and a good linear relationship is observed between current density and tellurium ion mass concentration. The linear relationship coefficient of the fitting curve is 0.973, indicating that the hollow ion-selective electrode prepared by the present invention has good electrochemical response characteristics and stability, and can be used for biochemical molecular detection, especially the precise detection of tellurium.

[0037] As attached Figure 7 As shown, it is the electrochemical curve of the hollow ion selective electrode detecting metallic mercury using the SWASV method, where Figure 7 (a) is the SWASV curve, Figure 7 (b) is a linear fitting plot. As can be seen from the figure, the gold electrode used as the electrode patch to detect metallic mercury ions produces a well-shaped curve, with a good linear relationship between current density and mercury ion mass concentration. The linear relationship coefficient of the fitting curve is 0.976, indicating that the hollow ion-selective electrode prepared by the present invention has good electrochemical response characteristics and stability, and can be used for biochemical molecular detection, especially the precise detection of metallic mercury.

[0038] As attached Figure 8 As shown, it is the electrochemical curve of the hollow ion selective electrode using the SWASV method to detect metallic arsenic, where Figure 8 (a) is the SWASV curve, Figure 8 (b) is a linear fitting graph. As can be seen from the figure, the curve obtained for detecting metallic arsenic ions using a gold electrode as the electrode patch is well-shaped, and the current density and arsenic ion mass concentration show a good linear relationship. The linear relationship coefficient of the fitting curve is 0.971, indicating that the hollow ion-selective electrode prepared by the present invention has good electrochemical response characteristics and stability, and can be used for biochemical molecular detection, especially the precise detection of metallic arsenic.

[0039] As attached Figure 9 As shown, the electrochemical curve of the hollow ion selective electrode using the SWASV method to simultaneously detect metal lead and metal zinc, where Figure 9 (a) is the SWASV curve, Figure 9 (b) is a linear fitting graph. As can be seen from the figure, the bismuth film electrode is used as the electrode patch to simultaneously detect metallic lead ions and zinc ions. The obtained curve has a good shape, and the current density and ion mass concentration show a good linear relationship. The linear relationship coefficient of the metallic lead ion fitting curve is 0.998, and the linear relationship coefficient of the metallic zinc ion fitting curve is 0.966. This shows that the hollow ion-selective electrode prepared by the present invention has good electrochemical response characteristics and stability, and can be used for biochemical molecular detection, especially for the simultaneous and accurate detection of metallic lead and metallic zinc.

[0040] As attached Figure 10 As shown, it is the electrochemical curve of the hollow ion selective electrode using the DPASV method to detect metallic arsenic, where Figure 10 (a) is the PASV curve, Figure 10 (b) is a linear fitting graph. As can be seen from the figure, the carbon electrode used as the electrode patch to detect metallic arsenic ions produces a well-shaped curve, with a good linear relationship between current density and arsenic ion mass concentration. The linear relationship coefficient of the fitting curve is 0.9892, indicating that the hollow ion-selective electrode prepared by the present invention has good electrochemical response characteristics and stability, and can be used for biochemical molecular detection, especially the precise detection of metallic arsenic.

[0041] As attached Figure 11 The figure shows the CV curve of the hollow ion-selective electrode prepared in Example 8 for detecting a phosphorus-containing electroless nickel plating solution. As can be seen from the figure, using a metal nickel sheet as the electrode patch and using the CV method to detect a phosphorus-containing electroless nickel plating solution, the obtained curve has a good shape and accurately reflects the reaction state of the plating solution. This shows that the hollow ion-selective electrode prepared by the present invention has good electrochemical response characteristics and stability, and can be used for electronic plating detection, especially for accurate detection of electroless plating solutions.

[0042] The beneficial effects of the present invention are:

[0043] (1) The present invention sets a three-electrode coplanar structure on the same plane, digs a hole in the detection core area to form a first hollow hole, and splits the working electrode into components, which are installed later as independent electrode patches. In order to avoid the electrode patch directly contacting the back substrate to produce a tiny gap, which in turn causes the detection liquid to overflow and the electrode reaction area to change and affect the detection accuracy, an insulating double-sided tape is used to fix the inside and fill the gap, and then a conductive tape is used to fix the outside for a second time to realize the transmission of electrical signals at the same time, thereby ensuring the sensitivity and accuracy of the electrode and solving the stability problem of the patch electrode.

[0044] (2) The present invention connects the back conductor line and the front conductive line through the conductive hole of the conductive substrate, and transmits the electrochemical reaction signal generated by the electrode patch in the first hollow hole area to the electrode pin through this path, and then transmits it out. While ensuring the sensitivity and accuracy of the electrode, it greatly reduces the area of ​​the three-electrode coplanar electrode, provides more conductive line layout solutions, greatly reduces the difficulty and cost of electrode electroplating processing, avoids secondary processing, optimizes the function and structural design of the standard electrode, and expands the application field of the electrode.

[0045] (3) The present invention achieves the purpose of selecting different electrode modification layers according to the characteristics of the detection target by setting the core detection area of ​​the working electrode as an independent electrode patch that can be freely replaced and selected. At the same time, the material and modification layer of the independent electrode patch serving as the core detection layer can be freely replaced and used immediately after replacement, making the selection of electrode patches more diverse, and achieving the purpose of detecting a variety of different biochemical molecules by replacing the electrode patch. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The invention is further described with reference to the accompanying drawings, but the embodiments in the accompanying drawings do not constitute any limitation to the invention. A person skilled in the art can obtain other drawings based on the following drawings without inventive effort.

[0047] Figure 1 This is a front view schematic diagram of a hollow ion selective electrode;

[0048] Figure 2 This is the back side of the hollow ion selective electrode. Figure 1 ;

[0049] Figure 3 This is the back side of the hollow ion selective electrode. Figure 2 ;

[0050] Figure 4 This is the back side of the hollow ion selective electrode. Figure 3 ;

[0051] Figure 5 1 is a schematic diagram of the side structure of a hollow ion selective electrode;

[0052] Figure 6 This is the electrochemical curve of the hollow ion selective electrode prepared in Example 1 for detecting metallic tellurium using the SWASV method;

[0053] Figure 7 This is the electrochemical curve of the hollow ion selective electrode prepared in Example 1 for detecting metallic mercury using the SWASV method;

[0054] Figure 8 This is the electrochemical curve of the hollow ion selective electrode prepared in Example 1 for detecting metallic arsenic using the SWASV method;

[0055] Figure 9 This is the electrochemical curve of the hollow ion selective electrode prepared in Example 4 for simultaneous detection of metallic lead and metallic zinc using the SWASV method;

[0056] Figure 10 This is the electrochemical curve of the hollow ion selective electrode prepared in Example 5 for detecting metallic arsenic using the DPASV method;

[0057] Figure 11 This is the CV curve of the hollow ion selective electrode prepared in Example 8 detecting a phosphorus-containing chemical nickel plating solution.

[0058] Legend:

[0059] 1. Electrode loading area; 11. First electrode layer; 12. Second electrode layer; 13. First hollow hole; 2. Front conductive circuit; 21. First circuit; 22. Second circuit; 23. Third circuit; 24. Through hole; 31. First pin; 32. Second pin; 33. Third pin; 4. Back conductive circuit; 41. Insulating double-sided tape; 42. Selective electrode patch; 43. Conductive tape. DETAILED DESCRIPTION

[0060] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail with reference to the following specific embodiments and the accompanying drawings.

[0061] Example 1

[0062] As attached Figure 1 The figure shows a hollow ion-selective electrode provided by the present invention, comprising a PET plate electrode substrate with electrode dimensions of 12 x 35 mm and a thickness of 0.35 mm. The substrate can be made of a flexible polymer material, or conventional electrode materials such as epoxy resin, ceramic, silicon, or glass.

[0063] A front conductive circuit 2 and an electrode loading area 1 are provided on the front side of the substrate. The electrode loading area 1 includes an electrode detection layer and a first hollow hole 13 penetrating the substrate. The radius of the first hollow hole 13 is set to 1 mm. The electrode detection layer includes a first electrode layer 11 and a second electrode layer 12 that are coplanar and not interconnected. A first hollow hole 13 is provided adjacent to the first electrode layer 11 and the second electrode layer 12. The first electrode layer 11 and the second electrode layer 12 are respectively connected to the front conductive circuit 2.

[0064] The front conductive circuit 2 includes a first circuit 21, a second circuit 22 and a third circuit 23 that are not connected to each other. The first circuit 21 is connected to the first electrode layer 11, the second circuit 22 is connected to the second electrode layer 12, and the third circuit 23 is arranged outside the first hollow hole 13 and is not in contact with it.

[0065] Three vias 24 are provided on the third circuit 23 . The vias 24 are also located on the back conductive circuit 4 on the back side of the substrate and are interconnected with the third circuit 23 through the vias 24 .

[0066] Electrode pins are also provided on the front surface of the substrate, including a first pin 31, a second pin 32 and a third pin 33 that are coplanar and equidistant, and are connected to the first circuit 21, the second circuit 22 and the third circuit 23 respectively.

[0067] like Figure 2 As shown, a first hollow hole 13 and a back conductive circuit 4 are coplanarly arranged on the back side of the substrate. A via 24 is provided on the back conductive circuit 4 . The front conductive circuit 2 and the back conductive circuit 4 are interconnected through the via 24 .

[0068] like Figures 3 to 5As shown, the back of the substrate is also provided with an insulating double-sided tape 41, a selective electrode patch 42, and a conductive tape 43. The selective electrode patch 42 is tightly adhered to the substrate via the insulating double-sided tape 41 and completely covers the position of the first hollow hole 13. A second hollow hole (not shown) is provided at the position corresponding to the first hollow hole 13. Its shape is concentric with the first hollow hole 13 and its size matches the size of the first hollow hole 13. The conductive tape 43 is provided above the selective electrode patch 42, fixing the selective electrode patch 42 to the back of the substrate, completely covering the selective electrode patch 42 and the area where the conductive hole 24 is located, and is in contact with and conductive to the back conductive circuit 4.

[0069] The surface of the front conductive circuit 2, electrode pins and the first electrode layer 11 of the electrode detection layer is coated with silver paste. The first electrode layer 11 is modified with carbon paste on the silver paste base, and the second electrode layer 12 is modified with silver-silver chloride paste with a thickness greater than 5μm.

[0070] The selective electrode patch 42 selects a gold electrode sheet with an overall thickness of 0.01 to 0.02 mm and an overall radius of 2 mm. The shape can be circular or rectangular, and can also be freely set. Its area is larger than the area of ​​the first hollow hole 13 and can completely cover it. In order to save costs, the gold electrode sheet uses a copper base, which is polished and plated with bright copper, then silver-plated, and finally gold-plated. Only the side in contact with the base layer can be processed on one side.

[0071] For ease of use, the front conductive circuit 2 of the substrate can be partially coated with ink, and then a second layer of ink can be coated on the periphery of the electrode loading area 1, leaving only the electrode detection layer and the first hollow hole 13 and the area where the electrode pins are located exposed. The thickness of each layer of ink is 10 to 20 μm.

[0072] Example 2

[0073] The present invention provides a hollow ion selective electrode, comprising a PET plate electrode substrate, the electrode size is 12x35mm, and the thickness is 0.35mm.

[0074] A front conductive circuit 2 and an electrode loading area 1 are provided on the front side of the substrate. The electrode loading area 1 includes an electrode detection layer and a first hollow hole 13 penetrating the substrate. The radius of the first hollow hole 13 is set to 1 mm. The electrode detection layer includes a first electrode layer 11 and a second electrode layer 12 that are coplanar and not interconnected. A first hollow hole 13 is provided adjacent to the first electrode layer 11 and the second electrode layer 12. The first electrode layer 11 and the second electrode layer 12 are respectively connected to the front conductive circuit 2.

[0075] The front conductive circuit 2 includes a first circuit 21, a second circuit 22 and a third circuit 23 that are not connected to each other. The first circuit 21 is connected to the first electrode layer 11, the second circuit 22 is connected to the second electrode layer 12, and the third circuit 23 is arranged outside the first hollow hole 13 and is not in contact with it.

[0076] Three vias 24 are provided on the third circuit 23 . The vias 24 are also located on the back conductive circuit 4 on the back side of the substrate and are interconnected with the third circuit 23 through the vias 24 .

[0077] Electrode pins are also provided on the front surface of the substrate, including a first pin 31, a second pin 32 and a third pin 33 that are coplanar and equidistant, and are connected to the first circuit 21, the second circuit 22 and the third circuit 23 respectively.

[0078] A first hollow hole 13 and a back conductive circuit 4 are coplanarly arranged on the back side of the substrate. A via hole 24 is provided on the back conductive circuit 4 . The front conductive circuit 2 and the back conductive circuit 4 are interconnected through the via hole 24 .

[0079] The back of the substrate is also provided with an insulating double-sided tape 41, a selective electrode patch 42, and a conductive tape 43. The selective electrode patch 42 is tightly adhered to the substrate via the insulating double-sided tape 41, completely covering the location of the first hollow hole 13. A second hollow hole is provided at the location corresponding to the first hollow hole 13, its shape concentric with the first hollow hole 13 and its size matches the first hollow hole 13. The conductive tape 43 is provided above the selective electrode patch 42, securing the selective electrode patch 42 to the back of the substrate, completely covering the selective electrode patch 42 and the area where the conductive hole 24 is located, and is in contact with the back conductive circuit 4.

[0080] The surface of the front conductive circuit 2, electrode pins and the first electrode layer 11 of the electrode detection layer is coated with silver paste. The first electrode layer 11 is modified with carbon paste on the silver paste base, and the second electrode layer 12 is modified with silver-silver chloride paste with a thickness greater than 5μm.

[0081] The selective electrode patch 42 is a silver electrode sheet, and its shape can be circular or rectangular, or can be freely set. Its area is larger than the area of ​​the first hollow hole 13 and can completely cover it.

[0082] For ease of use, the front conductive circuit 2 of the substrate can be partially coated with ink, and then a second layer of ink can be coated on the periphery of the electrode loading area 1, leaving only the electrode detection layer and the first hollow hole 13 and the area where the electrode pins are located exposed. The thickness of each layer of ink is 10 to 20 μm.

[0083] Example 3

[0084] The present invention provides a hollow ion selective electrode, comprising a PET plate electrode substrate, the electrode size is 12x35mm, and the thickness is 0.35mm.

[0085] A front conductive circuit 2 and an electrode loading area 1 are provided on the front side of the substrate. The electrode loading area 1 includes an electrode detection layer and a first hollow hole 13 penetrating the substrate. The radius of the first hollow hole 13 is set to 1 mm. The electrode detection layer includes a first electrode layer 11 and a second electrode layer 12 that are coplanar and not interconnected. A first hollow hole 13 is provided adjacent to the first electrode layer 11 and the second electrode layer 12. The first electrode layer 11 and the second electrode layer 12 are respectively connected to the front conductive circuit 2.

[0086] The front conductive circuit 2 includes a first circuit 21, a second circuit 22 and a third circuit 23 that are not connected to each other. The first circuit 21 is connected to the first electrode layer 11, the second circuit 22 is connected to the second electrode layer 12, and the third circuit 23 is arranged outside the first hollow hole 13 and is not in contact with it.

[0087] Three vias 24 are provided on the third circuit 23 . The vias 24 are also located on the back conductive circuit 4 on the back side of the substrate and are interconnected with the third circuit 23 through the vias 24 .

[0088] Electrode pins are also provided on the front surface of the substrate, including a first pin 31, a second pin 32 and a third pin 33 that are coplanar and equidistant, and are connected to the first circuit 21, the second circuit 22 and the third circuit 23 respectively.

[0089] A first hollow hole 13 and a back conductive circuit 4 are coplanarly arranged on the back side of the substrate. A via hole 24 is provided on the back conductive circuit 4 . The front conductive circuit 2 and the back conductive circuit 4 are interconnected through the via hole 24 .

[0090] The back of the substrate is also provided with an insulating double-sided tape 41, a selective electrode patch 42, and a conductive tape 43. The selective electrode patch 42 is tightly adhered to the substrate via the insulating double-sided tape 41, completely covering the location of the first hollow hole 13. A second hollow hole is provided at the location corresponding to the first hollow hole 13, its shape concentric with the first hollow hole 13 and its size matches the first hollow hole 13. The conductive tape 43 is provided above the selective electrode patch 42, securing the selective electrode patch 42 to the back of the substrate, completely covering the selective electrode patch 42 and the area where the conductive hole 24 is located, and is in contact with the back conductive circuit 4.

[0091] The surface of the front conductive circuit 2, electrode pins and the first electrode layer 11 of the electrode detection layer is coated with silver paste. The first electrode layer 11 is modified with carbon paste on the silver paste base, and the second electrode layer 12 is modified with silver-silver chloride paste with a thickness greater than 5μm.

[0092] The selective electrode patch 42 is a platinum electrode sheet, which can be circular or rectangular in shape, or can be freely set. Its area is larger than the area of ​​the first hollow hole 13 and can completely cover it.

[0093] For ease of use, the conductive line 2 on the front side of the substrate can be partially coated with ink, and then the periphery of the electrode loading area 1 can be coated with a second layer of ink, leaving only the electrode detection layer and the first hollow hole 13 and the area where the electrode pin is located exposed. The thickness of each layer of ink is 10 to 20 μm.

[0094] Example 4

[0095] The present invention provides a hollow ion selective electrode, comprising a PET plate electrode substrate, the electrode size is 12x35mm, and the thickness is 0.35mm.

[0096] A front conductive circuit 2 and an electrode loading area 1 are provided on the front side of the substrate. The electrode loading area 1 includes an electrode detection layer and a first hollow hole 13 penetrating the substrate. The radius of the first hollow hole 13 is set to 1 mm. The electrode detection layer includes a first electrode layer 11 and a second electrode layer 12 that are coplanar and not interconnected. A first hollow hole 13 is provided adjacent to the first electrode layer 11 and the second electrode layer 12. The first electrode layer 11 and the second electrode layer 12 are respectively connected to the front conductive circuit 2.

[0097] The front conductive circuit 2 includes a first circuit 21, a second circuit 22 and a third circuit 23 that are not connected to each other. The first circuit 21 is connected to the first electrode layer 11, the second circuit 22 is connected to the second electrode layer 12, and the third circuit 23 is arranged outside the first hollow hole 13 and is not in contact with it.

[0098] Three vias 24 are provided on the third circuit 23 . The vias 24 are also located on the back conductive circuit 4 on the back side of the substrate and are interconnected with the third circuit 23 through the vias 24 .

[0099] Electrode pins are also provided on the front surface of the substrate, including a first pin 31, a second pin 32 and a third pin 33 that are coplanar and equidistant, and are connected to the first circuit 21, the second circuit 22 and the third circuit 23 respectively.

[0100] A first hollow hole 13 and a back conductive circuit 4 are coplanarly arranged on the back side of the substrate. A via hole 24 is provided on the back conductive circuit 4 . The front conductive circuit 2 and the back conductive circuit 4 are interconnected through the via hole 24 .

[0101] The back of the substrate is also provided with an insulating double-sided tape 41, a selective electrode patch 42, and a conductive tape 43. The selective electrode patch 42 is tightly adhered to the substrate via the insulating double-sided tape 41, completely covering the location of the first hollow hole 13. A second hollow hole is provided at the location corresponding to the first hollow hole 13, its shape concentric with the first hollow hole 13 and its size matches the first hollow hole 13. The conductive tape 43 is provided above the selective electrode patch 42, securing the selective electrode patch 42 to the back of the substrate, completely covering the selective electrode patch 42 and the area where the conductive hole 24 is located, and is in contact with the back conductive circuit 4.

[0102] The surface of the front conductive circuit 2, electrode pins and the first electrode layer 11 of the electrode detection layer is coated with silver paste. The first electrode layer 11 is modified with carbon paste on the silver paste base, and the second electrode layer 12 is modified with silver-silver chloride paste with a thickness greater than 5μm.

[0103] The selective electrode patch 42 selects a bismuth electrode sheet. Specifically, a bismuth film can be modified on the surface of the reaction surface of the electrode sheet. The shape of the electrode sheet can be circular or rectangular, and can also be freely set. Its area is larger than the area of ​​the first hollow hole 13 and can completely cover it.

[0104] For ease of use, the front conductive circuit 2 of the substrate can be partially coated with ink, and then a second layer of ink can be coated on the periphery of the electrode loading area 1, leaving only the electrode detection layer and the first hollow hole 13 and the area where the electrode pins are located exposed. The thickness of each layer of ink is 10 to 20 μm.

[0105] Example 5

[0106] The present invention provides a hollow ion selective electrode, comprising a PET plate electrode substrate, the electrode size is 12x35mm, and the thickness is 0.35mm.

[0107] A front conductive circuit 2 and an electrode loading area 1 are provided on the front side of the substrate. The electrode loading area 1 includes an electrode detection layer and a first hollow hole 13 penetrating the substrate. The radius of the first hollow hole 13 is set to 1 mm. The electrode detection layer includes a first electrode layer 11 and a second electrode layer 12 that are coplanar and not interconnected. A first hollow hole 13 is provided adjacent to the first electrode layer 11 and the second electrode layer 12. The first electrode layer 11 and the second electrode layer 12 are respectively connected to the front conductive circuit 2.

[0108] The front conductive circuit 2 includes a first circuit 21, a second circuit 22 and a third circuit 23 that are not connected to each other. The first circuit 21 is connected to the first electrode layer 11, the second circuit 22 is connected to the second electrode layer 12, and the third circuit 23 is arranged outside the first hollow hole 13 and is not in contact with it.

[0109] Three vias 24 are provided on the third circuit 23 . The vias 24 are also located on the back conductive circuit 4 on the back side of the substrate and are interconnected with the third circuit 23 through the vias 24 .

[0110] Electrode pins are also provided on the front surface of the substrate, including a first pin 31, a second pin 32 and a third pin 33 that are coplanar and equidistant, and are connected to the first circuit 21, the second circuit 22 and the third circuit 23 respectively.

[0111] A first hollow hole 13 and a back conductive circuit 4 are coplanarly arranged on the back side of the substrate. A via hole 24 is provided on the back conductive circuit 4 . The front conductive circuit 2 and the back conductive circuit 4 are interconnected through the via hole 24 .

[0112] The back of the substrate is also provided with an insulating double-sided tape 41, a selective electrode patch 42, and a conductive tape 43. The selective electrode patch 42 is tightly adhered to the substrate via the insulating double-sided tape 41, completely covering the location of the first hollow hole 13. A second hollow hole is provided at the location corresponding to the first hollow hole 13, its shape concentric with the first hollow hole 13 and its size matches the first hollow hole 13. The conductive tape 43 is provided above the selective electrode patch 42, securing the selective electrode patch 42 to the back of the substrate, completely covering the selective electrode patch 42 and the area where the conductive hole 24 is located, and is in contact with the back conductive circuit 4.

[0113] The surface of the front conductive circuit 2, electrode pins and the first electrode layer 11 of the electrode detection layer is coated with silver paste. The first electrode layer 11 is modified with carbon paste on the silver paste base, and the second electrode layer 12 is modified with silver-silver chloride paste with a thickness greater than 5μm.

[0114] The selective electrode patch 42 is a carbon electrode sheet, and the material can be carbon-related materials including graphene. The shape can be circular or rectangular, and can also be freely set. Its area is larger than the area of ​​the first hollow hole 13 and can completely cover it.

[0115] For ease of use, the front conductive circuit 2 of the substrate can be partially coated with ink, and then a second layer of ink can be coated on the periphery of the electrode loading area 1, leaving only the electrode detection layer and the first hollow hole 13 and the area where the electrode pins are located exposed. The thickness of each layer of ink is 10 to 20 μm.

[0116] Example 6

[0117] The present invention provides a hollow ion selective electrode, comprising a PET plate electrode substrate, the electrode size is 12x35mm, and the thickness is 0.35mm.

[0118] A front conductive circuit 2 and an electrode loading area 1 are provided on the front side of the substrate. The electrode loading area 1 includes an electrode detection layer and a first hollow hole 13 penetrating the substrate. The radius of the first hollow hole 13 is set to 1 mm. The electrode detection layer includes a first electrode layer 11 and a second electrode layer 12 that are coplanar and not interconnected. A first hollow hole 13 is provided adjacent to the first electrode layer 11 and the second electrode layer 12. The first electrode layer 11 and the second electrode layer 12 are respectively connected to the front conductive circuit 2.

[0119] The front conductive circuit 2 includes a first circuit 21, a second circuit 22 and a third circuit 23 that are not connected to each other. The first circuit 21 is connected to the first electrode layer 11, the second circuit 22 is connected to the second electrode layer 12, and the third circuit 23 is arranged outside the first hollow hole 13 and is not in contact with it.

[0120] Three vias 24 are provided on the third circuit 23 . The vias 24 are also located on the back conductive circuit 4 on the back side of the substrate and are interconnected with the third circuit 23 through the vias 24 .

[0121] Electrode pins are also provided on the front surface of the substrate, including a first pin 31, a second pin 32 and a third pin 33 that are coplanar and equidistant, and are connected to the first circuit 21, the second circuit 22 and the third circuit 23 respectively.

[0122] A first hollow hole 13 and a back conductive circuit 4 are coplanarly arranged on the back side of the substrate. A via hole 24 is provided on the back conductive circuit 4 . The front conductive circuit 2 and the back conductive circuit 4 are interconnected through the via hole 24 .

[0123] The back of the substrate is also provided with an insulating double-sided tape 41, a selective electrode patch 42, and a conductive tape 43. The selective electrode patch 42 is tightly adhered to the substrate via the insulating double-sided tape 41, completely covering the location of the first hollow hole 13. A second hollow hole is provided at the location corresponding to the first hollow hole 13, its shape concentric with the first hollow hole 13 and its size matches the first hollow hole 13. The conductive tape 43 is provided above the selective electrode patch 42, securing the selective electrode patch 42 to the back of the substrate, completely covering the selective electrode patch 42 and the area where the conductive hole 24 is located, and is in contact with the back conductive circuit 4.

[0124] The surface of the front conductive circuit 2, electrode pins and the first electrode layer 11 of the electrode detection layer is coated with silver paste. The first electrode layer 11 is modified with carbon paste on the silver paste base, and the second electrode layer 12 is modified with silver-silver chloride paste with a thickness greater than 5μm.

[0125] The selective electrode patch 42 is a chromium electrode sheet. Specifically, a chromium film can be modified on the surface of the reaction surface of the electrode sheet. The shape of the electrode sheet can be circular or rectangular, and can also be freely set. Its area is larger than the area of ​​the first hollow hole 13 and can completely cover it.

[0126] For ease of use, the front conductive circuit 2 of the substrate can be partially coated with ink, and then a second layer of ink can be coated on the periphery of the electrode loading area 1, leaving only the electrode detection layer and the first hollow hole 13 and the area where the electrode pins are located exposed. The thickness of each layer of ink is 10 to 20 μm.

[0127] Example 7

[0128] The present invention provides a hollow ion selective electrode, comprising a PET plate electrode substrate, the electrode size is 12x35mm, and the thickness is 0.35mm.

[0129] A front conductive circuit 2 and an electrode loading area 1 are provided on the front side of the substrate. The electrode loading area 1 includes an electrode detection layer and a first hollow hole 13 penetrating the substrate. The radius of the first hollow hole 13 is set to 1 mm. The electrode detection layer includes a first electrode layer 11 and a second electrode layer 12 that are coplanar and not interconnected. A first hollow hole 13 is provided adjacent to the first electrode layer 11 and the second electrode layer 12. The first electrode layer 11 and the second electrode layer 12 are respectively connected to the front conductive circuit 2.

[0130] The front conductive circuit 2 includes a first circuit 21, a second circuit 22 and a third circuit 23 that are not connected to each other. The first circuit 21 is connected to the first electrode layer 11, the second circuit 22 is connected to the second electrode layer 12, and the third circuit 23 is arranged outside the first hollow hole 13 and is not in contact with it.

[0131] Three vias 24 are provided on the third circuit 23 . The vias 24 are also located on the back conductive circuit 4 on the back side of the substrate and are interconnected with the third circuit 23 through the vias 24 .

[0132] Electrode pins are also provided on the front surface of the substrate, including a first pin 31, a second pin 32 and a third pin 33 that are coplanar and equidistant, and are connected to the first circuit 21, the second circuit 22 and the third circuit 23 respectively.

[0133] A first hollow hole 13 and a back conductive circuit 4 are coplanarly arranged on the back side of the substrate. A via hole 24 is provided on the back conductive circuit 4 . The front conductive circuit 2 and the back conductive circuit 4 are interconnected through the via hole 24 .

[0134] The back of the substrate is also provided with an insulating double-sided tape 41, a selective electrode patch 42, and a conductive tape 43. The selective electrode patch 42 is tightly adhered to the substrate via the insulating double-sided tape 41, completely covering the location of the first hollow hole 13. A second hollow hole is provided at the location corresponding to the first hollow hole 13, its shape concentric with the first hollow hole 13 and its size matches the first hollow hole 13. The conductive tape 43 is provided above the selective electrode patch 42, securing the selective electrode patch 42 to the back of the substrate, completely covering the selective electrode patch 42 and the area where the conductive hole 24 is located, and is in contact with the back conductive circuit 4.

[0135] The surface of the front conductive circuit 2, electrode pins and the first electrode layer 11 of the electrode detection layer is coated with silver paste. The first electrode layer 11 is modified with carbon paste on the silver paste base, and the second electrode layer 12 is modified with silver-silver chloride paste with a thickness greater than 5μm.

[0136] The selective electrode patch 42 is a nickel electrode sheet. Specifically, a chromium film can be modified on the surface of the reaction surface of the electrode sheet. The shape of the electrode sheet can be circular or rectangular, and can also be freely set. Its area is larger than the area of ​​the first hollow hole 13 and can completely cover it.

[0137] For ease of use, the front conductive circuit 2 of the substrate can be partially coated with ink, and then a second layer of ink can be coated on the periphery of the electrode loading area 1, leaving only the electrode detection layer and the first hollow hole 13 and the area where the electrode pins are located exposed. The thickness of each layer of ink is 10 to 20 μm.

[0138] Example 8

[0139] The present invention provides a hollow ion selective electrode, comprising a PET plate electrode substrate, the electrode size is 12x35mm, and the thickness is 0.35mm.

[0140] A front conductive circuit 2 and an electrode loading area 1 are provided on the front side of the substrate. The electrode loading area 1 includes an electrode detection layer and a first hollow hole 13 penetrating the substrate. The radius of the first hollow hole 13 is set to 1 mm. The electrode detection layer includes a first electrode layer 11 and a second electrode layer 12 that are coplanar and not interconnected. A first hollow hole 13 is provided adjacent to the first electrode layer 11 and the second electrode layer 12. The first electrode layer 11 and the second electrode layer 12 are respectively connected to the front conductive circuit 2.

[0141] The front conductive circuit 2 includes a first circuit 21, a second circuit 22 and a third circuit 23 that are not connected to each other. The first circuit 21 is connected to the first electrode layer 11, the second circuit 22 is connected to the second electrode layer 12, and the third circuit 23 is arranged outside the first hollow hole 13 and is not in contact with it.

[0142] Three vias 24 are provided on the third circuit 23 . The vias 24 are also located on the back conductive circuit 4 on the back side of the substrate and are interconnected with the third circuit 23 through the vias 24 .

[0143] Electrode pins are also provided on the front surface of the substrate, including a first pin 31, a second pin 32 and a third pin 33 that are coplanar and equidistant, and are connected to the first circuit 21, the second circuit 22 and the third circuit 23 respectively.

[0144] A first hollow hole 13 and a back conductive circuit 4 are coplanarly arranged on the back side of the substrate. A via hole 24 is provided on the back conductive circuit 4 . The front conductive circuit 2 and the back conductive circuit 4 are interconnected through the via hole 24 .

[0145] The back of the substrate is also provided with an insulating double-sided tape 41, a selective electrode patch 42, and a conductive tape 43. The selective electrode patch 42 is tightly adhered to the substrate via the insulating double-sided tape 41, completely covering the location of the first hollow hole 13. A second hollow hole is provided at the location corresponding to the first hollow hole 13, its shape concentric with the first hollow hole 13 and its size matches the first hollow hole 13. The conductive tape 43 is provided above the selective electrode patch 42, securing the selective electrode patch 42 to the back of the substrate, completely covering the selective electrode patch 42 and the area where the conductive hole 24 is located, and is in contact with the back conductive circuit 4.

[0146] The surface of the front conductive circuit 2, electrode pins and the first electrode layer 11 of the electrode detection layer is coated with silver paste. The first electrode layer 11 is modified with carbon paste on the silver paste base, and the second electrode layer 12 is modified with silver-silver chloride paste with a thickness greater than 5μm.

[0147] The selective electrode patch 42 is based on a gold electrode sheet, which is modified with active enzyme substances. The electrode sheet in contact with the electrode substrate can be modified on one side. The shape of the substrate can be circular or rectangular, or can be set freely. Its area is larger than the area of ​​the first hollow hole 13 and can completely cover it.

[0148] For ease of use, the front conductive circuit 2 of the substrate can be partially coated with ink, and then a second layer of ink can be coated on the periphery of the electrode loading area 1, leaving only the electrode detection layer and the first hollow hole 13 and the area where the electrode pins are located exposed. The thickness of each layer of ink is 10 to 20 μm.

[0149] Example 9

[0150] Biochemical molecular detection applications of hollow ion selective electrodes:

[0151] The hollow ion selective electrodes prepared in Examples 1, 4, 5, 6, and 7 can detect several heavy metal ions, including but not limited to the following categories:

[0152]

[0153]

[0154] Specifically, the hollow ion selective electrode loaded with gold electrode sheet prepared in Example 1 was prepared with formic acid-ammonium formate buffer solution with a pH value of 4.0, and the deposition potential was set to -1.3 V and the deposition time was 180 s to obtain Figure 6 Shown is the electrochemical curve for detecting metallic tellurium.

[0155] Specifically, the hollow ion selective electrode loaded with gold electrode prepared in Example 1 was prepared with acetic acid-sodium acetate buffer with a pH value of 4.5, and the deposition potential was set to -0.6 V and the deposition time was 60 s to obtain Figure 7 Shown is the electrochemical curve for detecting metallic mercury.

[0156] Specifically, the hollow ion selective electrode loaded with gold electrode prepared in Example 1 was prepared with 1M hydrochloric acid buffer, the deposition potential was set to -0.2V, the deposition time was set to 180s, and the obtained Figure 8 Shown is the electrochemical curve for detecting metallic arsenic.

[0157] Specifically, the hollow ion selective electrode loaded with bismuth electrode sheet prepared in Example 4 was prepared with acetic acid-sodium acetate buffer, and the deposition time was set to 180s to obtain Figure 9 The electrochemical curves for the simultaneous detection of metallic lead and metallic zinc are shown.

[0158] Specifically, the hollow ion selective electrode loaded with carbon electrode sheet prepared in Example 5 was prepared with a phosphate buffer having a pH value of 7.0, and the deposition potential was set to -0.8 V and the deposition time was 180 s to obtain Figure 10 Shown is the electrochemical curve for detecting metallic arsenic.

[0159] Specifically, the hollow ion selective electrode loaded with nickel electrode sheet prepared in Example 7 was used to detect phosphorus-containing chemical nickel plating solution with the Yuxin portable electrochemical workstation to obtain Figure 11 The electrochemical CV curves are shown.

[0160] 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 embodied 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 illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0161] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This description is for clarity only. Those skilled in the art should consider this specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art. Technical details not described in detail in this invention can be implemented by any existing technology in the art. In particular, all technical features not described in detail in this invention can be implemented by any existing technology.

Claims

1. A hollow ion-selective electrode, comprising an electrode substrate, characterized in that: A front conductive circuit (2) and an electrode loading area (1) are provided on the front surface of the substrate, a conductive hole (24) is provided on the front conductive circuit (2), and the electrode loading area (1) includes an electrode detection layer and a first hollow hole (13) penetrating the substrate; the first hollow hole (13) and a back conductive circuit (4) are coplanarly provided on the back surface of the substrate, the conductive hole (24) is provided on the back conductive circuit (4), and the front conductive circuit (2) and the back conductive circuit (4) are interconnected through the conductive hole (24); an insulating double-layer structure is also provided on the back surface of the substrate. The selective electrode patch (42) and the conductive tape (43) are provided. The selective electrode patch (42) is tightly attached to the substrate through the insulating double-sided tape (41) and completely covers the position of the first hollow hole (13). The insulating double-sided tape (41) is provided with a second hollow hole at a position corresponding to the first hollow hole (13). The conductive tape (43) is arranged above the selective electrode patch (42) to fix the selective electrode patch (42) on the back side of the substrate and is in contact with the back conductive circuit (4).

2. The hollow ion selective electrode according to claim 1, characterized in that: The electrode detection layer comprises a first electrode layer (11) and a second electrode layer (12) which are coplanarly arranged and not interconnected, the first hollow hole (13) being arranged adjacent to the first electrode layer (11) and the second electrode layer (12), and the first electrode layer (11) and the second electrode layer (12) being respectively connected to the front conductive circuit (2).

3. The hollow ion selective electrode according to claim 2, characterized in that: The front conductive circuit (2) comprises a first circuit (21), a second circuit (22), and a third circuit (23) which are not connected to each other, the first circuit (21) being connected to the first electrode layer (11), the second circuit (22) being connected to the second electrode layer (12), and the third circuit (23) being arranged outside the first hollow hole (13).

4. The hollow ion selective electrode according to claim 3, characterized in that: One or more vias (24) are provided on the third circuit (23); the vias (24) are also located on the back conductive circuit (4) on the back side of the substrate and are interconnected with the third circuit (23) through the vias (24).

5. The hollow ion selective electrode according to claim 3, characterized in that: The front surface of the substrate is also provided with electrode pins, including a first pin (31), a second pin (32) and a third pin (33) that are coplanar and equidistant, and are respectively connected to the first circuit (21), the second circuit (22) and the third circuit (23).

6. The hollow ion selective electrode according to claim 1, characterized in that: The surfaces of the front conductive circuit (2), electrode pins, electrode detection layer and back conductive circuit (4) are modified with a metal layer as a base metal, and the metal type includes silver.

7. The hollow ion selective electrode according to claim 1, characterized in that: The surface of the first electrode layer (11) of the electrode detection layer is further provided with a modification layer, and the material of the modification layer includes carbon.

8. The hollow ion selective electrode according to claim 1, characterized in that: The surface of the second electrode layer (12) of the electrode detection layer is provided with a modification layer, and the modification layer comprises a silver-silver chloride layer.

9. The hollow ion selective electrode according to claim 1, characterized in that: The second hollow hole formed on the insulating double-sided adhesive tape (41) is concentric in shape with the first hollow hole (13), and its size is consistent with that of the first hollow hole (13).

10. The hollow ion selective electrode according to claim 1, characterized in that: The conductive tape (43) completely covers the area where the selective electrode patch (42) and the conducting hole (24) are located.

11. The hollow ion selective electrode according to claim 1, characterized in that: The selective electrode patch (42) may be made of materials including carbon and metals, and the metal materials include gold, silver, platinum, bismuth, chromium, copper, and nickel.

12. The hollow ion selective electrode according to claim 1, characterized in that: The side of the selective electrode patch (42) in contact with the back of the substrate can be modified with an ion selective modification layer. The specific material of the ion selective modification layer can be arbitrarily replaced according to detection requirements, including metal film, enzyme, and porous metal.

13. Use of the hollow ion selective electrode according to any one of claims 1 to 12 in biochemical molecule detection.

Images