TWI695166B - A multi-ion sensing electrode array chip and sensing device thereof - Google Patents

Abstract

The present invention provides a multi-ion sensing electrode array chip comprising a solid-state insulating substrate, a reference electrode, and at least two ion-selective electrodes. The present invention also provides an ion sensing device, which comprising: a multi-electrode sensing electrode array chip as described above; a detector, comprising: a hardware integrated system for obtaining sensing signals from the reference electrode and/or the ion selective electrode; and a fixture for housing the hardware integrated system and/or placing the multi-sensing electrode array chip.

Description

Multi-ion sensing electrode array test piece and sensing device

The invention provides a multi-ion sensing electrode array test strip. The multi-ion sensing electrode array test strip includes: a solid insulating substrate; at least two ion selective electrodes, which are arranged on the substrate and used for sensing ions in the sample And a reference electrode, which is disposed on the substrate and used to provide a reference point for measuring the potential of the at least two ion selective electrodes. The present invention further provides an ion sensing device, including: a multi-ion sensing electrode array test piece as described above; a detector, which includes: a hardware integration system for obtaining the reference electrode and/or The sensing signal of the ion selective electrode; and a carrier for receiving the hardware integration system and/or placing the multi-ion sensing electrode array test strip.

Ion-selective electrodes (ISE) is a converter that converts the concentration of specific ions dissolved in a solution into potential, and is a common method for quantitative and selective detection of ions. With the development of miniaturization technology for portable miniature electrochemical sensors, the electrodes themselves must also be miniaturized. The ion selective electrode has the advantages of miniaturization, easy instrumentation and suitable for the design of automated systems. In addition to the applications in analytical chemistry and biochemistry, biophysical research, it can also be applied to, for example, human body fluids, agricultural hydroponic liquids, home The detection of pH and various ions in any liquid environment such as water quality, aquaculture and aquarium industry is quite extensive. However, the existing ion selective electrodes can only detect a single ion in a single detection, and want to detect multiple species in the sample at the same time Ions need to use multiple ion-selective electrodes at the same time, it is difficult to obtain a reduction in size for the convenience of use. In addition, the design of existing ion-selective electrode modules is also limited in size, energy supply and information transmission. Therefore, a Emerging ion-sensing electrode device and its matching module design to solve the above-mentioned problems of unfavorable use.

The invention provides a multi-ion sensing electrode array test strip. The multi-ion sensing electrode array test strip includes: a solid insulating substrate; at least two ion selective electrodes, which are arranged on the substrate and used for sensing ions in the sample The at least two ion selective electrodes each include: an ion selective electrode conductive layer, which is disposed on the substrate and has an ion selective electrode conductive layer electrode terminal and an ion selective electrode conductive layer connection terminal, wherein the ion selective electrode is conductive The layer electrode terminal is used to transmit the electrical signal detected by the multi-ion sensing electrode array test piece, the ion selective electrode conductive layer connection terminal is used to connect a detector; an ion selective electrode conductive layer is disposed on the ion selection The electrode terminal of the ion selective electrode conductive layer of the electrode conductive layer is used to convert the ion signal into an electrical signal and/or improve the measurement stability; and an ion selective electrode screening layer disposed on the ion selective electrode conductive layer Upper, for sensing ion concentration; and a reference electrode, which is disposed on the substrate and used to provide a reference point for potential measurement of the at least two ion selective electrodes. The reference electrode includes: a reference electrode conductive layer, which It is arranged on the substrate and has a reference electrode conductive layer electrode terminal and a reference electrode conductive layer connection terminal, wherein the reference electrode conductive layer electrode terminal is used to transmit the electrical signal of the reference electrode, and the reference electrode conductive layer connection terminal is used to Connected to a detector; and a reference electrode transparent layer, which is disposed on the conductive layer of the reference electrode to assist the overall reference electrode to reach chemical equilibrium, wherein the at least two ion selective electrodes each detect a specific one of the samples Ion, each ion selection The specific ion detected by the electrode is different.

In an embodiment, the reference electrode may further include a reference electrode conductive layer disposed between the electrode end of the reference electrode conductive layer of the reference electrode conductive layer and the reference electrode transparent layer to increase the reference potential Of stability.

In an embodiment, the ion selective electrode conductive layer may further include an ion selective electrode conductive layer wire region disposed between the electrode terminal of the ion selective electrode conductive layer and the connection terminal of the ion selective electrode conductive layer.

In another embodiment, the surface of the conductive layer of the ion selective electrode is insulated.

In an embodiment. The material of the ion selective electrode conductive layer has the characteristics of high hydrophobicity, high capacitance value, or both high hydrophobicity and high capacitance value.

In an embodiment, examples of the sample include (but are not limited to) a true solution, a colloidal solution, and a suspension.

In an embodiment, exemplary materials of the solid insulating substrate include (but are not limited to) polyethylene terephthalate (PET), polycarbonate, polyester, polyether, polyamine, polychloride , Polyimide, polyvinyl chloride, flexible polyethylene, glass, fiberglass board, alumina and ceramics.

In one embodiment, exemplary materials of the ion selective electrode conductive layer include (but are not limited to) carbon paste, gold paste, silver paste, carbon silver paste, conductive carbon paste, indium tin oxide, metal thin film, and semiconductor Wait.

In an embodiment, exemplary materials of the ion selective electrode conductive layer include (but are not limited to) conductive polymers, graphite, and carbon materials.

In an embodiment, exemplary materials of the conductive polymer include (but are not limited to) polyaniline (PANI), poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (Polypyrrole), and poly Thiophene (Polythiophene) and so on.

In an embodiment, exemplary materials of the carbon material include (but are not limited to) nano carbon tubes and graphene.

In an embodiment, examples of the carbon nanotubes include, but are not limited to, single-layer nanotubes, multi-layer nanotubes, and functionalized nanotubes.

In an embodiment, the ion selective electrode screening layer includes an ion carrier, a plasticizer, and a polymer material.

In another embodiment, the ion selective electrode screening layer may further include an anion/cation adsorbent.

In another embodiment, the ionophore refers to a substance that has an affinity for a specific ion.

In another embodiment, examples of the ion-selective electrode ionophore include (but are not limited to) Tetraoctylammonium nitrate, Tetraoctylammonium nitrate, Nonactin, and bis[4-(1,1,3, 3-tetramethylbutyl)phenyl] calcium phosphate (Calcium bis-{[4-(1,1,3,3-tetramethylbutyl)phenyl]-phosphate}), N,N,N',N'-tetracyclo Hexyl-3-oxapentanediamide [N,N,N',N'-tetracyclohexyl-3-oxapentanediamide], N,N-dicyclohexyl- N',N'-Dioctadecyl-3-oxapentane-1,5-diamide (N,N-dicyclohexyl-N',N'-dioctadecyl-3-oxapentane-1,5-diamide) , Valinomycin, Benzo-15-crown-5, 1,3[bis(3-phenylthioureamethyl)]benzene(1,3-[Bis (3-phenylthioureidomethyl)]benzene), N,N'-bis(sullylidene)-o-phenylenediamine vanadium(IV) oxidation complex (N,N'-Bis(salicylidene)-o-phenylenediamine Vanadium( IV)oxide Complex), 4-tertiary butyl calix[4]arene-tetraacetic acid-tetraethyl ester ([4-tert-butyylcalix[4]arene-tetraacetic acid tetraethyl ester]) and N,N'-diphenyl Methyl-diphenyl-1,2-phenylene-dioxydiacetamide (N, N'-dibenzyl-N, N'-diphenyl-1,2-phenylene-dioxydiacetamide), etc.

In another embodiment, the anti-anion/cation adsorbent can resist ion adsorption opposite to the sensed ion.

In another embodiment, examples of the anti-anion/cation adsorbent include (but are not limited to) potassium tetrakis(4-chlorophenyl) borate, tetrakis(3,5 -Sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and tridodecylmethylammonium chloride, etc.

In another embodiment, examples of the plasticizer include (but are not limited to) 2-nitrophenyl octyl ether, dibutyl phthalate, triphenyl phosphate Ester (Tripentyl phosphate), 1-chloronaphthalene (1-chloronaphthalene), bis (2-ethylhexyl) sebacate (bis (2-ethylhexyl) sebacate) and dioctyl adipate (Diethyl adipate) and so on.

In another embodiment, examples of the polymer material include (but are not limited to) polyvinyl chloride (PVC), silicone rubber, acrylic polymer, and urethane ( urethane) etc.

In an embodiment, the reference electrode conductive layer may further include a reference electrode conductive layer wire region disposed between the reference electrode conductive layer electrode terminal and the reference electrode conductive layer connection terminal.

In another embodiment, the surface of the conductive layer of the reference electrode conductive layer is insulated.

In one embodiment, exemplary materials of the reference electrode conductive layer include (but are not limited to) carbon paste, gold paste, silver paste, carbon-silver mixed paste, conductive carbon paste, indium tin oxide, metal thin film, semiconductor, etc. .

In another embodiment, exemplary materials of the reference electrode conductive layer include (but are not limited to) silver/silver chloride, conductive polymers, and carbon materials.

In another embodiment, the reference electrode transparent layer includes an ionic compound, a plasticizer, an organic solvent, and a polymer material.

In another embodiment, examples of the ionic compound include (but are not limited to) ionic liquids, molten salts and salts.

In another embodiment, examples of the plasticizer include (but are not limited to) 2-nitrophenyl octyl ether, dibutyl phthalate, triphenyl phosphate Tripentyl phosphate, 1-chloronaphthalene, sebacic acid Diisooctyl ester (bis (2-ethylhexyl) sebacate) and dioctyl adipate (Diethyladipate) and so on.

In another embodiment, examples of the polymer material include (but are not limited to) polyvinyl chloride (PVC), silicone rubber, acrylic polymer, and urethane ( urethane) etc.

In another embodiment, the ionic compound is used to increase stability.

The present invention also provides an ion sensing device, including: a multi-ion sensing electrode array test piece as described above; and a detector, which includes: a hardware integration system for obtaining the reference electrode and/or Or the sensing signal of the ion selective electrode; and a carrier for receiving the hardware integration system and/or placing the multi-ion sensing electrode array test strip.

In one embodiment, the hardware integration system includes a micro-processing chip for controlling multiplexers, converting analog digital signals, and/or data transmission; a microprocessor operating module for carrying the micro-processor Processing chip, a hardware module power supply, and a button to activate the multiplexer switching function; a signal conditioning circuit for amplifying the voltage signal received from the ion selective electrode, and/or providing a bias voltage; and a connection It is used to connect the ion selective electrode circuit and the signal conditioning circuit.

In one embodiment, the data transmission is transmitted to one or more servers via wireless or wired.

In an embodiment, the wireless transmission module is transmitted via Bluetooth.

In an embodiment, the wireless transmission module is a Wi-Fi transmission module.

In an embodiment, examples of the server include (but are not limited to) a network Servers, cloud servers, computers, mobile devices, and instruments.

In an embodiment, the server calibrates, presents, and/or counts the sensing data through an application program.

In one embodiment, the ion sensing device can be used for monitoring of agricultural hydroponic cultivation liquid.

In one embodiment, the ion sensing device can be used for monitoring water quality at home.

In one embodiment, the ion sensing device can be used for medical care and monitoring of body fluids.

In one embodiment, the ion sensing device can be used for aquaculture industry water quality monitoring and/or aquarium industry water quality management.

In one embodiment, the ion sensing device can be used for the detection of harmful chemicals, pesticide residues and/or heavy metal residues in food.

Examples of the ion sensing device of the present invention that can sense ions include (but are not limited to) nitrate, ammonium, potassium, calcium, magnesium, phosphorus, sulfur, sodium, chlorine, hydrogen, and heavy metals.

10: Multi-ion sensing electrode array test strip

20: substrate

30: ion selective electrode

301: ion selective electrode conductive layer

3011: Ion selective electrode conductive layer electrode terminal

3012: ion selective electrode lead area

3013: Ion selective electrode connection terminal

302: ion selective electrode conductive layer

303: ion selective electrode screening layer screening layer

304: Ion selective electrode insulating layer

40: Reference electrode

401: Reference electrode conductive layer

4011: Reference electrode tip

4012: Reference electrode lead area

4013: Reference electrode connection

402: Reference electrode conductive layer

403: Reference electrode transparent layer

404: Reference electrode insulation

50: Tester

501: Hardware integration system

502: Vehicle

Figure 1. Structure diagram of multi-ion sensing electrode array test strip.

Figure 2. Schematic diagram of the layered structure and manufacturing process of the multi-ion sensing electrode array test piece.

Figure 3. Structure diagram of vehicle detector

Figure 4. The top view and the bottom view of the PCB design drawing of the microprocessor operation module. The arrows and circles in the view of the PCB of the microprocessor operation module indicate the connection to the microprocessor.

Figure 5. The circuit schematic of the microprocessor operating module.

Figure 6. The top view and the bottom view of the PCB design of the signal conditioning circuit. The arrows and circles in the view on the PCB of the signal conditioning circuit indicate the signal conditioning chip locations such as the ADG708, precision amplifier LMP7721, and amplifier LMP7715.

Figure 7. The circuit schematic of the signal conditioning circuit.

Figure 8. Top and bottom views of the PCB design of the connector.

Figure 9 Description of the actual measurement steps of the ion sensing device: (a) low concentration standard solution correction (b) medium concentration standard solution correction (c) high concentration standard solution correction (d) real-field measurement.

Fig. 10. Comparison of measured concentration of hydroponic nutrient solution and actual sample concentration of ion sensing device. The gray above is the actual sample concentration, and the black is the measured concentration. It can be seen that the measured concentration of the ion sensing device and the concentration (in millimoles (mM)) are consistent with the trend of change; the horizontal axis of the following figure is the actual sample concentration (The unit is millimolar concentration (mM)), and the vertical axis is the measured concentration (unit is millimolar concentration (mM)). It can be seen that the correlation between the actual sample concentration and the measured concentration is extremely high. (a) nitrate NO ₃ ^- (b) ammonium NH ₄ ⁺ (c) Potassium K ⁺ (d) calcium Ca ^2+.

The following examples only represent various aspects and features of the present invention and do not limit the scope of the present invention.

Example 1: Preparation of multi-ion sensing electrode array test strip (10)

The multi-ion sensing electrode array test piece (10) of the present invention is insulated with a solid state The material is used as the substrate (20), which may be polyethylene terephthalate, aluminum oxide, plastic or ceramic sheets, etc.; with conductive ink, it may be carbon powder, graphite powder or metal particles, etc., through a layer to design the shape of the electrode layer The screen holes cover the insulating base plate. The multi-ion sensing electrode array test strip includes a reference electrode (30) and at least one ion selective electrode (40), as shown in FIGS. 1 and 2.

The structural design of the ion selective electrode (30) includes an ion selective electrode conductive layer (301), an ion selective electrode conductive layer (302), an ion selective electrode screening layer (303), and an ion selective electrode insulating layer (304). As shown in Figure 2, first, silver paste or carbon paste is overlaid on the base plate (20) by screen printing to form an ion selective electrode conductive layer (301), and graphite, carbon or other conductive polymers The material is covered on the ion selective electrode conductive layer electrode terminal (3011) of the ion selective electrode conductive layer (301) to make an ion selective electrode conductive layer (302); the ion selective electrode conductive layer (302) is covered above to be combined with polyvinyl chloride, etc. Ion selective electrode screening layer (303) made of polymer material, ion carrier, and plasticizer; except that the terminal of the ion selective electrode conductive layer (3011) and the ion selective electrode conductive layer connecting terminal (3013) are coated with insulating glue The area (conductor area of the conductive layer of the ion selective electrode, 3012) forms an insulating layer (304) of the ion selective electrode, and the conductive area (3012) of the conductive layer of the enclosed ion selective electrode communicates with the outside world.

The structural design of the reference electrode (40) includes a reference electrode conductive layer (401), a reference electrode conductive layer (402), a reference electrode transparent layer (403), and a reference electrode insulating layer (404). As shown in Fig. 2, first, silver paste or carbon paste is overlaid on the base plate (20) by screen printing to form a reference electrode conductive layer (401), and the silver/silver chloride paste is screen printed The reference electrode conductive layer (402) is formed by covering the reference electrode conductive layer electrode end (4011) of the reference electrode conductive layer (401); the reference electrode conductive layer (402) is covered with a polymer material such as polyvinyl chloride, Ionic liquid, plasticizer and The reference electrode transparent layer (403) made of organic solvent; the area except the reference electrode conductive layer electrode terminal (4011) and the reference electrode isoelectric layer connection terminal (4013) coated with insulating glue (reference electrode conductive layer wire area, 4012) The reference electrode insulation layer (404) is formed, and the reference electrode wire area (4012) is closed to communicate with the outside world.

Example 2: Structure and function of the detector

As shown in FIG. 3, the ion sensing device of the present invention includes: a multi-ion sensing electrode array test strip (10) as described above; and a detector (50, FIG. 3), which includes: a hard A body integration system (501) for obtaining the sensing signal of the reference electrode and/or the ion selective electrode; and a carrier (502) for accommodating the hardware integration system and/or placing the multi-ion sensing Electrode array test piece. The hardware integration system (501) is composed of a three-layer circuit PCB board plus a micro-processing chip (CC2650) for arithmetic communication. The three-layer circuit PCB board is a microprocessor operation module from top to bottom (Figure 4, figure 5). Signal conditioning circuit (Figure 6, Figure 7) and connector (Figure 8). The microprocessor chip is used to control the multiplexer, convert analog digital signals, and/or data transmission; the microprocessor operation module is used to carry the microprocessor chip (CC2650), a hardware module power supply, And a button to activate the switch function of the multiplexer; the signal conditioning circuit consists of a signal conditioning chip such as the ADG708 multiplexer, the precision amplifier LMP7721, the amplifier LMP7715, and other circuit components, which are used to amplify the voltage signal received from the ion selective electrode , And/or provide bias; and a connector for connecting the ion selective electrode circuit and the signal conditioning circuit. The hardware integration system can transmit the sensed concentration signal to the matched mobile device to correct or present the sensed signal.

Example 3: Application software of ion sensing device

As shown in Fig. 9, through the mobile device mobile application (APP), the sensing data transmitted by multiple electrodes can be quickly corrected, and the concentration sense of multiple ions can be displayed simultaneously 测结果。 Test results. The measurement of the ion sensing device is achieved through the following steps: 1. The device is calibrated with a low concentration standard solution; 2. The device is calibrated with a medium concentration standard solution; 3. The device is calibrated with a high concentration standard solution; 4 .Measure the sample with the calibration device.

Example 4: Performance test of ion selective electrode

The comparison result between the measured concentration of the hydroponic cultivation liquid of the ion sensing device and the actual sample concentration is shown in FIG. 10. The gray above is the actual sample concentration, and the black is the measured concentration. It can be seen that the measured concentration of the ion sensing device and the concentration (in millimoles (mM)) are consistent with the trend of change; the horizontal axis of the following figure is the actual sample concentration (The unit is millimolar concentration (mM)), and the vertical axis is the measured concentration (unit is millimolar concentration (mM)). It can be seen that the correlation between the actual sample concentration and the measured concentration is extremely high. (a) nitrate NO ₃ ^- (b) ammonium NH ₄ ⁺ (c) Potassium K ⁺ (d) calcium Ca ^2+.

10‧‧‧Multi-ion sensing electrode array test strip

20‧‧‧ substrate

30‧‧‧Ion selective electrode

301‧‧‧Ion selective electrode conductive layer

3011‧‧‧Ion selective electrode conductive layer electrode terminal

3012‧‧‧Ion selective electrode conductive layer wire area

3013‧‧‧Ion selective electrode conductive layer connection end

302‧‧‧Ion selective electrode conductive layer

303‧‧‧Ion selective electrode screening layer

304‧‧‧Ion selective electrode insulating layer

40‧‧‧ Reference electrode

401‧‧‧Reference electrode conductive layer

4011‧‧‧Reference electrode conductive layer electrode terminal

4012‧‧‧Reference electrode conductive layer conductor area

4013‧‧‧ Reference electrode conductive layer connection terminal

402‧‧‧Reference electrode conductive layer

403‧‧‧ Reference electrode transparent layer

404‧‧‧Reference electrode insulation

50‧‧‧detector

501‧‧‧Hardware integration system

502‧‧‧vehicle

Claims (10)

A multi-ion sensing electrode array test strip. The multi-ion sensing electrode array test strip includes: a solid insulating substrate; at least two ion-selective electrodes, which are disposed on the substrate and used to sense ions in the sample. The two ion selective electrodes each include: an ion selective electrode conductive layer disposed on the substrate, having an ion selective electrode conductive layer electrode terminal and an ion selective electrode conductive layer connection terminal, wherein the ion selective electrode conductive layer electrode terminal It is used to transmit the electrical signal detected by the multi-ion sensing electrode array test piece. The ion selective electrode conductive layer connection end is used to connect a detector; an ion selective electrode conductive layer is disposed on the ion selective electrode conductive layer On the electrode end of the ion selective electrode for converting ion signals into electrical signals and/or improving measurement stability; and an ion selective electrode screening layer disposed on the ion selective electrode conductive layer for sensing Measuring ion concentration; and a reference electrode disposed on the substrate to provide a reference point for measuring the potential of the at least two ion-selective electrodes. The reference electrode includes: a reference electrode conductive layer disposed on the substrate , With a reference electrode conductive layer electrode terminal and a reference electrode conductive layer connection terminal, wherein the reference electrode conductive layer electrode terminal is used to transfer the electrical signal of the reference electrode, the reference electrode conductive layer connection terminal is used to connect a detector; And a reference electrode transparent layer, which is disposed on the reference electrode conductive layer to assist the overall reference The electrodes reach chemical equilibrium, wherein the at least two ion-selective electrodes each detect a specific ion in the sample, and the specific ions detected by the ion-selective electrodes are not the same. For example, the multi-ion sensing electrode array test piece of claim 1, wherein the reference electrode may further include a reference electrode conductive layer, which is disposed between the reference electrode conductive layer and the reference electrode transparent layer for Improve the stability of the reference potential. For example, the multi-ion sensing electrode array test piece of patent application item 1, wherein the ion-selective electrode conductive layer may further include an ion-selective electrode conductive layer wire region, which is disposed at the electrode end of the ion-selective electrode conductive layer and the ions Select between the connecting ends of the electrode conductive layers. For example, the test piece of the multi-ion sensing electrode array of claim 3, in which the surface of the conductive area of the ion selective electrode conductive layer is insulated. For example, the multi-ion sensing electrode array test piece of patent application item 1, wherein the material of the ion selective electrode conductive layer has the characteristics of high hydrophobicity, high capacitance, or both high hydrophobicity and high capacitance. For example, the multi-ion sensing electrode array test piece of patent application item 1, wherein the reference electrode conductive layer may further include a reference electrode conductive layer wire region, which is disposed at the electrode end of the reference electrode conductive layer and the reference electrode conductive layer Between the connected ends. For example, the multi-ion sensing electrode array test piece of the patent application item 1, wherein the surface of the conductive area of the conductive layer of the reference electrode is insulated. An ion sensing device, including: A multi-ion sensing electrode array test piece as described in item 1 of the scope of patent application; and a detector comprising: a hardware integrated system for obtaining the sense of the reference electrode and/or the ion selective electrode Measurement signal, which includes a micro-processing chip for controlling multiplexers, converting analog digital signals, and/or data transmission; a microprocessor operating module for carrying the micro-processing chip, and a hardware module power supply Supply, and a button to activate the multiplexer switching function; a signal conditioning circuit to amplify the voltage signal received from the ion-selective electrode and/or provide a bias voltage; and a connector to connect the ion-selector An electrode circuit and the signal conditioning circuit; and a carrier for receiving the hardware integration system and/or placing the multi-ion sensing electrode array test piece. The ion sensing device as described in item 8 of the patent application, wherein the data transmission is transmitted to one or more servers through wireless or wired. The ion sensing device as described in item 9 of the patent application scope, wherein the server calibrates, presents and/or counts the sensing data through an application program.

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