CN112683975A - Interdigital microelectrode array electrochemical sensor, preparation method, application and special test box - Google Patents

Interdigital microelectrode array electrochemical sensor, preparation method, application and special test box Download PDF

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Publication number
CN112683975A
CN112683975A CN202011508466.4A CN202011508466A CN112683975A CN 112683975 A CN112683975 A CN 112683975A CN 202011508466 A CN202011508466 A CN 202011508466A CN 112683975 A CN112683975 A CN 112683975A
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aluminum
microelectrode array
microelectrode
interdigital
electrochemical sensor
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李明吉
张天润
李红姬
刘丹丹
李翠平
李爱学
王桂莲
龙拥兵
杨保和
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South China Agricultural University
Tianjin University of Technology
Beijing Research Center for Information Technology in Agriculture
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South China Agricultural University
Tianjin University of Technology
Beijing Research Center for Information Technology in Agriculture
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Abstract

The invention provides an interdigital microelectrode array electrochemical sensor, a preparation method, application and a special test box, and relates to the technical field of sensors. The interdigital aluminum microelectrode array is formed by combining three groups of aluminum microelectrode arrays in an interdigital mode, each group of aluminum microelectrode array is an electrode, and the three groups of aluminum microelectrode arrays form a three-electrode system. The electrochemical sensor provided by the invention takes the interdigital aluminum microelectrode array as a chip, and the interdigital aluminum microelectrode array has high three-electrode staggered density and a planar structure and is suitable for conventional in-vitro detection; the interdigital aluminum microelectrode array can be in a sheet shape and is convenient to carry. The special test box provided by the invention has the advantages of simple structure, abundant raw material sources and capability of accurately and quickly testing the performance of the electrochemical sensor.

Description

Interdigital microelectrode array electrochemical sensor, preparation method, application and special test box
Technical Field
The invention relates to the technical field of sensors, in particular to an interdigital microelectrode array electrochemical sensor, a preparation method, application and a special test box.
Background
The electrochemical sensor has the advantages of fast response, high sensitivity, low cost, simple operation, easy miniaturization and the like, but the electrochemical sensor does not realize portable online detection in actual operation, is more suitable for an in-vitro detection method, and can not well contact a detected object to realize living body monitoring. Therefore, there is a need to develop a portable electrochemical biosensor suitable for in vivo monitoring.
Disclosure of Invention
In view of the above, the present invention provides an interdigitated microelectrode array electrochemical sensor, a method for manufacturing the interdigitated microelectrode array electrochemical sensor, an application of the interdigitated microelectrode array electrochemical sensor, and a test kit for the interdigitated microelectrode array electrochemical sensor. The interdigital microelectrode array electrochemical sensor provided by the invention can be in a patch type, is convenient to carry, and is directly attached to living animals for diagnosis of non-diseases and detection of treatment purposes.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an interdigital microelectrode array electrochemical sensor which comprises an interdigital aluminum microelectrode array, wherein the interdigital aluminum microelectrode array is formed by combining three groups of aluminum microelectrode arrays in an interdigital mode and is respectively a first aluminum microelectrode array, a second aluminum microelectrode array and a third aluminum microelectrode array; each group of aluminum microelectrode array is an electrode, and the three groups of aluminum microelectrode arrays form a three-electrode system comprising a working electrode, a counter electrode and a reference electrode.
Preferably, the first aluminum microelectrode array comprises a first trunk and a first comb array positioned on one side of the first trunk; the second aluminum microelectrode array comprises a second trunk and second comb-shaped arrays positioned on two sides of the second trunk, and the third aluminum microelectrode array comprises a third trunk and a third comb-shaped array positioned on one side of the third trunk; the second comb-shaped arrays on two sides of the second main stem are respectively interdigital to the first comb-shaped array on one side of the first main stem and the third comb-shaped array on one side of the third main stem.
Preferably, the counter electrode is a platinum-modified group of aluminum microelectrode arrays, the reference electrode is a gold-modified group of aluminum microelectrode arrays, and the working electrode is a to-be-detected-substance molecularly imprinted polymer-modified group of aluminum microelectrode arrays.
Preferably, the counter electrode is a group of aluminum microelectrode arrays modified by platinum and a deposition aid, the reference electrode is a group of aluminum microelectrode arrays modified by gold and a deposition aid, and the working electrode is a group of aluminum microelectrode arrays modified by a substance to be detected, namely a molecularly imprinted polymer.
Preferably, the substance to be detected is lysine, glucose or dopamine.
Preferably, the deposition aid is dopamine.
Preferably, the electrochemical sensor further comprises a metal housing, a flip-top lid mated with the metal housing; four pins are arranged at the outer bottom of the metal shell; the interdigital aluminum microelectrode array is arranged in the central area of the inner bottom of the metal shell; and three of the four pins are respectively connected with the three groups of aluminum microelectrode arrays of the interdigital aluminum microelectrode array through wires.
The invention also provides a preparation method of the interdigital microelectrode array electrochemical sensor, which comprises the following steps:
sputtering an aluminum film on a substrate, and photoetching the aluminum film to obtain an interdigital aluminum microelectrode array;
and respectively depositing a counter electrode material, a reference electrode material and a working electrode material on the three groups of aluminum microelectrode arrays of the interdigital aluminum microelectrode array to obtain the electrochemical sensor.
The invention also provides an application of the interdigital microelectrode array electrochemical sensor or the interdigital microelectrode array electrochemical sensor prepared by the preparation method in the technical scheme in the field of molecular detection.
The invention also provides a special test box of the interdigital microelectrode array electrochemical sensor in the technical scheme, which comprises a cuboid plastic body, wherein four small holes are drilled on one surface of the cuboid plastic body, and the positions and the sizes of the small holes respectively correspond to the positions and the sizes of four pins of the interdigital microelectrode array electrochemical sensor; copper sheets are padded at the bottoms of the holes of the small holes, and binding posts are led out by screws; the cuboid plastic body is made of polytetrafluoroethylene.
The invention provides an interdigital microelectrode array electrochemical sensor which comprises an interdigital aluminum microelectrode array, wherein the interdigital aluminum microelectrode array is formed by combining three groups of aluminum microelectrode arrays in an interdigital mode and is respectively a first aluminum microelectrode array, a second aluminum microelectrode array and a third aluminum microelectrode array; each group of aluminum microelectrode array is an electrode, and the three groups of aluminum microelectrode arrays form a three-electrode system comprising a working electrode, a counter electrode and a reference electrode. The electrochemical sensor provided by the invention takes the interdigital aluminum microelectrode array as a chip, and the interdigital aluminum microelectrode array has high three-electrode staggered density and a planar structure, so that the interdigital aluminum microelectrode array is suitable for being attached to the surface of a living organism to carry out non-disease diagnosis and treatment purpose detection of various compounds, and is also suitable for a conventional in-vitro detection method; meanwhile, the interdigital aluminum microelectrode array can be in a sheet shape, so that the interdigital microelectrode array chemical sensor becomes a patch type and is convenient to carry.
The invention also provides the special test box for the interdigital microelectrode array electrochemical sensor, which has the advantages of simple structure, rich raw material sources and capability of accurately and quickly testing the performance of the interdigital microelectrode array electrochemical sensor.
Drawings
FIG. 1 is a schematic structural diagram of an interdigitated aluminum microelectrode array provided in the present invention, wherein A is a first aluminum microelectrode array, A1 is a first backbone, and A2 is a first comb-shaped array; b is a second aluminum microelectrode array, B1 is a second backbone, B2 is a second comb array; c is a third aluminum microelectrode array, C1 is a third backbone, C2 is a third comb array;
FIG. 2 is an optical microscope photograph of an array of interdigitated aluminum microelectrodes used in an example of the present invention;
FIG. 3 is a top view of a metal housing used in an embodiment of the present invention, where 1, 2, 3 and 4 respectively represent four pins located at the outer bottom of the metal housing;
FIG. 4 is a photograph of an electrochemical sensor provided in accordance with an embodiment of the present invention;
FIG. 5 is a physical diagram of the test box specially used for the interdigitated microelectrode array electrochemical sensor provided by the present invention;
FIG. 6 is a deposition curve of a gold modified aluminum microelectrode array;
FIG. 7 is an SEM image of gold obtained by gold modification of an aluminum microelectrode array;
FIG. 8 is a deposition curve of a polyacrylamide-dopamine modified aluminum microelectrode array;
FIG. 9 is an SEM image of the deposition of polyacrylamide-dopamine on an aluminum microelectrode array modified by polyacrylamide-dopamine;
FIG. 10 is a deposition curve of a platinum modified aluminum microelectrode array;
FIG. 11 is an SEM image of platinum obtained from a platinum modified aluminum microelectrode array;
FIG. 12 is an SEM image of platinum-dopamine obtained by platinum-dopamine modified aluminum microelectrode array;
fig. 13 is a DPV curve for dopamine samples, lysine samples and PBS buffer solution.
Detailed Description
The invention provides an interdigital microelectrode array electrochemical sensor which comprises an interdigital aluminum microelectrode array, wherein the interdigital aluminum microelectrode array is formed by combining three groups of aluminum microelectrode arrays in an interdigital mode and is respectively a first aluminum microelectrode array, a second aluminum microelectrode array and a third aluminum microelectrode array; each group of aluminum microelectrode array is an electrode, and the three groups of aluminum microelectrode arrays form a three-electrode system comprising a working electrode, a counter electrode and a reference electrode.
The interdigital microelectrode array electrochemical sensor provided by the invention comprises an interdigital aluminum microelectrode array. FIG. 1 is a schematic diagram of the structure of an interdigitated aluminum microelectrode array provided by the invention. In the present invention, the first aluminum microelectrode array a includes a first trunk a1 and a first comb array a2 located on the first trunk a1 side; the second aluminum microelectrode array B comprises a second backbone B1 and a second comb array B2 positioned on both sides of a second backbone B1, and the third aluminum microelectrode array C comprises a third backbone C1 and a third comb array C2 positioned on one side of the third backbone C1; the second comb array B2 on both sides of the second main stem B1 is respectively interdigitated with the first comb array a2 on one side of the first main stem a1 and the third comb array C2 on one side of the third main stem C1.
In a specific embodiment of the invention, the area of the interdigitated aluminum microelectrode array is preferably 2.42mm × 4.2mm, the interdigitated aluminum microelectrode array preferably has 933 fingers, wherein the width of 908 fingers is preferably 1 μm and the width of 25 fingers is preferably 4.7 μm, and the optical microscopic image of the interdigitated aluminum microelectrode array is shown in FIG. 2.
In the invention, the counter electrode is preferably a platinum-modified group of aluminum microelectrode arrays, the reference electrode is preferably a gold-modified group of aluminum microelectrode arrays, and the working electrode is preferably a to-be-detected object molecularly imprinted polymer-modified group of aluminum microelectrode arrays.
In the invention, the counter electrode is preferably a group of aluminum microelectrode arrays modified by platinum and a deposition aid, the reference electrode is preferably a group of aluminum microelectrode arrays modified by gold and a deposition aid, and the working electrode is preferably a group of aluminum microelectrode arrays modified by a substance to be detected, namely a molecularly imprinted polymer. In the invention, the deposition aid, gold, the deposition aid and the platinum modified aluminum microelectrode array are used as counter electrodes or reference electrodes, so that the sensitivity of the electrochemical sensor can be improved.
The type of the analyte is not particularly limited, and the analyte may be selected according to a substance to be actually detected, and is particularly preferably dopamine, lysine or glucose.
The interdigital microelectrode array electrochemical sensor provided by the invention preferably further comprises a metal shell; the material of the metal shell is preferably copper; four pins are arranged at the outer bottom of the metal shell; three of the four pins are respectively connected with the three groups of aluminum microelectrode arrays of the interdigital aluminum microelectrode array through wires; the interdigital aluminum microelectrode array is preferably positioned in the central area of the bottom in the metal shell. In an embodiment of the present invention, a top view of the metal housing is shown in fig. 3, where 1, 2, 3, and 4 respectively represent four pins located at the outer bottom of the metal housing; the size of the metal shell is preferably 10mm multiplied by 14.5mm multiplied by 5.1mm in length, width and height; the distance between the pin 1 and the pin 2 is preferably 5.0mm, and the distance between the pin 1 and the pin 4 is preferably 9.5 mm; the height of the pins is preferably 5.0 mm; the shape of the pins is preferably a cylinder, the diameter of the cylinder preferably being 0.7 mm.
The interdigital microelectrode array electrochemical sensor provided by the invention preferably further comprises a flip-type cover matched with the metal shell.
FIG. 4 is a photograph of an interdigitated microelectrode array electrochemical sensor provided in an embodiment of the present invention.
The interdigital microelectrode array electrochemical sensor provided by the invention comprises an interdigital aluminum microelectrode array, and the interdigital aluminum microelectrode array has high three-electrode staggered density and a planar structure, so that the interdigital microelectrode array is suitable for being attached to the surface of a living organism to carry out non-disease diagnosis and treatment purpose detection of various compounds, and is also suitable for a conventional in-vitro detection method; meanwhile, the interdigital microelectrode array is generally in a sheet shape and is convenient to carry.
The invention also provides a preparation method of the interdigital microelectrode array electrochemical sensor, which comprises the following steps:
sputtering an aluminum film on a substrate, and photoetching the aluminum film to obtain an interdigital aluminum microelectrode array;
and respectively depositing counter electrode substances, reference electrode substances and working electrode substances on the three groups of aluminum microelectrode arrays of the interdigital aluminum microelectrode array to obtain the interdigital microelectrode array electrochemical sensor.
The method comprises the steps of sputtering an aluminum film on a substrate, and photoetching the aluminum film to obtain the interdigital aluminum microelectrode array. The method for sputtering the aluminum film is not particularly limited, and sputtering means known to those skilled in the art may be used. In the present invention, the thickness of the aluminum film is preferably 120 to 130 nm. The parameters of the photoetching are not particularly limited, and the photoetching technical means known to those skilled in the art can be adopted as long as the interdigital aluminum microelectrode array can be obtained.
After the interdigital aluminum microelectrode array is obtained, counter electrode substances, reference electrode substances and working electrode substances are respectively deposited on the three groups of aluminum microelectrode arrays of the interdigital aluminum microelectrode array, and the electrochemical sensor is obtained.
In the present invention, when the counter electrode is preferably platinum, the parameters for depositing platinum particularly preferably include: the deposition solution used preferably comprises chloroplatinic acid; the deposition solution is preferably composed of chloroplatinic acid aqueous solution and PBS buffer solution; in the deposition solution, the concentration of chloroplatinic acid is preferably 0.02 mol/L; the deposition solution preferably further comprisesA deposition aid, preferably dopamine; the concentration of the deposition aid is preferably 10-4mol/L. In the present invention, the deposition mode is preferably a multi-potential step method, and the parameters of the multi-potential step method preferably include: the step potential of the first step is-0.2-0V, the deposition time of the first step is 0.3-0.7 s, and the preferable time is 0.5 s; the step potential of the second step is-1.5 to-2.5V, and the preferable step potential is-2.0V; the second-step deposition time is 3-7 s, and the preferable time is 5 s; the number of deposition turns is 20-30. After the deposition is finished, the invention preferably further comprises taking the device out of the deposition solution, then washing the device by using ultrapure water, and then drying the device for 5min at normal temperature.
In the present invention, when the reference electrode is gold, the parameters of the deposited gold preferably include: the deposition solution preferably comprises tetrachloroauric acid, and is preferably prepared by mixing a tetrachloroauric acid solution and a PBS buffer solution; the concentration of the tetrachloroauric acid in the deposition solution is preferably 10-3mol/L; the deposition solution preferably further comprises a deposition aid; the deposition aid is preferably dopamine, and the concentration of the deposition aid is preferably 10-4mol/L. In the present invention, the deposition mode is preferably a multi-potential step method, and the parameters of the multi-potential step method preferably include: the step potential of the first step is-0.2-0V, the deposition time of the first step is 0.3-0.7 s, and the preferable time is 0.5 s; the step potential of the second step is-1.5 to-2.5V, and the preferable step potential is-2.0V; the second-step deposition time is 3-7 s, and the preferable time is 5 s; the number of deposition turns is preferably 20 to 50 turns, and more preferably 30 turns. After the deposition is finished, the invention preferably further comprises taking the device out of the deposition solution, then washing the device by using ultrapure water, and then drying the device for 5min at normal temperature.
In the present invention, when the analyte molecule is preferably dopamine, the parameters for depositing dopamine-polymer preferably include: the deposition solution used preferably comprises dopamine and polymeric monomers; the concentration of dopamine and polymer monomer in the deposition solution is preferably 10-3mol/L. In the present invention, the deposition is preferably performed by a multi-potential step method, and the preferred parameters of the multi-potential step method include:the first step potential is 1.5-2.5V, and the preferable voltage is 2.0V; the first-step deposition time is 0.5-1.5 s, and the preferable time is 1 s; the step potential of the second step is-0.1 to-0.3V, and the preferable step potential is-0.2V; the second-step deposition time is 0.1-0.3 s, and the preferable time is 0.2 s; the number of deposition turns is 20-70 turns, and more preferably 30-60 turns. After the deposition is finished, the invention preferably further comprises taking the device out of the deposition solution, then washing the device by using ultrapure water, and then drying the device for 5min at normal temperature.
In the present invention, the parameters of the molecular imprinting preferably include: the eluent is preferably ethanol water solution, and the volume concentration of the ethanol water solution is preferably 50%; the method of elution is preferably a time-current curve method, the parameters of which include: the low potential is-0.2 to-0.3V, and the number of cleaning turns is 30 to 50 turns. And after the molecular imprinting is finished, taking out the device from the deposition solution, then washing the device by using ultrapure water, and then drying the device for 5min at normal temperature.
In the invention, the preparation method preferably further comprises assembling the metal shell, the flip cover and the interdigitated aluminum microelectrode array to obtain the electrochemical sensor. The assembly method of the present invention is not particularly limited, and the technical means known to those skilled in the art may be adopted.
The invention also provides an application of the interdigital microelectrode array electrochemical sensor or the interdigital microelectrode array electrochemical sensor prepared by the preparation method in the technical scheme in the field of molecular detection.
In the present invention, when the interdigitated microelectrode array electrochemical sensor is applied to molecular detection, it preferably comprises the following steps:
connecting three pins of the interdigital microelectrode array electrochemical sensor with a counter electrode end, a reference electrode end and an alligator clip of a working port of an electrochemical workstation respectively;
and dropping the substance to be detected on an interdigital aluminum microelectrode array of the interdigital microelectrode array electrochemical sensor to realize the detection of molecules.
The invention also provides a special test box of the interdigital microelectrode array electrochemical sensor, which comprises a cuboid plastic body, wherein four small holes are drilled on one surface of the cuboid plastic body, and the positions and the sizes of the small holes respectively correspond to the positions and the sizes of four pins of the interdigital microelectrode array electrochemical sensor; and a copper sheet is padded at the bottom of the hole of the small hole, and a binding post is led out by adopting a screw.
The test box provided by the invention comprises a rectangular plastic body, wherein the material of the rectangular plastic body is preferably polytetrafluoroethylene; four small holes are drilled in one surface of the cuboid plastic body, the positions and the sizes of the small holes correspond to those of four pins of the electrochemical sensor respectively, and copper sheets are padded at the bottoms of the small holes and lead out binding posts by screws. In a specific embodiment of the present invention, the rectangular parallelepiped plastic body preferably has a length, a width and a height of 20mm × 20mm × 15 mm; the small hole is preferably arranged on one surface of the cuboid plastic body, the diameter of which is 20mm multiplied by 20 mm; in a specific embodiment of the invention, the number of the small holes is preferably 6, wherein the positions of the 4 small holes are matched with the positions of the four pins of the interdigitated microelectrode array electrochemical sensor so as to enable the four pins to enter; and the support columns are inserted into the other 2 small holes to support the test box. In the present invention, the diameter of the small hole is independently preferably 1mm, and the depth is preferably 0.7 mm. In the present invention, the physical diagram of the special test box is shown in fig. 5.
In the invention, the use method of the test box special for the interdigitated microelectrode array electrochemical sensor preferably comprises the following steps:
inserting four pins of the interdigital microelectrode array electrochemical sensor into corresponding small holes of the special test box, and connecting the binding posts with each port of an electrochemical workstation, a potentiostat and a signal generator for testing.
The method for testing is not particularly limited, and a sensor performance testing method known to those skilled in the art can be adopted.
The interdigitated microelectrode array electrochemical sensor and the preparation method and application thereof, and the special test kit provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
EXAMPLE 1 preparation of interdigitated microelectrode array
Sputtering an aluminum film on the substrate, wherein the thickness of the aluminum film is 120 nm; by adopting the photoetching technology, an interdigital aluminum microelectrode array is prepared, the area of the interdigital aluminum microelectrode array is 2.42mm multiplied by 4.2mm, the interdigital aluminum microelectrode array has 933 fingers, the width of 908 fingers is 1 μm, the width of 25 fingers is 4.7 μm, and the optical microscope image of the interdigital aluminum microelectrode array is shown in figure 2.
Providing a metal shell according to fig. 3 and 4, wherein the metal shell has the dimensions of length, width and height of 10mm multiplied by 14.5mm multiplied by 5.1 mm; wherein, the distance between the pin 1 and the pin 2 is 5.0mm, and the distance between the pin 1 and the pin 4 is 9.5 mm; the height of the pins is 5.0 mm; the pin is in the shape of a cylinder, and the diameter of the cylinder is 0.7 mm.
Cleaning an interdigital aluminum microelectrode array: and (4) washing the interdigital aluminum microelectrode array by using ultrapure water and naturally drying.
Cleaning of the platinum electrode: selecting a platinum wire with the diameter of 0.5-1 mm as a counter electrode, polishing the platinum wire by using alumina powder before use, then immersing the platinum wire into a nitric acid aqueous solution with the volume concentration of 50 percent for ultrasonic cleaning for 5min, and then sequentially performing ultrasonic cleaning for 5min by using ultrapure water, absolute ethyl alcohol and ultrapure water.
Cleaning of the reference electrode: the Saturated Calomel Electrode (SCE) was rinsed with ultra pure water for future use.
The beaker and the volumetric flask are sequentially subjected to ultrasonic cleaning by using ultrapure water, absolute ethyl alcohol and ultrapure water, and then the beaker and the volumetric flask are placed on a glass instrument dryer to be dried for 5 min.
The buffer solution is a 0.1mol/L mixed solution of 0.1mol/L anhydrous disodium hydrogen phosphate and anhydrous sodium dihydrogen phosphate, and is hereinafter referred to as PBS buffer solution.
Example 2 preparation of gold-modified microelectrode array
Weighing 0.0339gThe tetrachloroauric acid is placed in a 10mL volumetric flask, PBS buffer solution with pH value of 7 is added for constant volume, and the solution is prepared into the solution with the concentration of 10-2And (3) mol/L tetrachloroauric acid solution.
Taking 2.5mL of 10 concentration by using a pipette-2Putting the tetrachloroauric acid solution into a 25mL volumetric flask, adding PBS buffer solution for dilution and volume fixing to obtain the solution with the concentration of 10-3A tetrachloroauric acid solution of mol/L.
Opening an electrochemical workstation, starting a multi-potential step method, putting the interdigital aluminum microelectrode array into the central area of the inner bottom of the metal shell, connecting a pin 1 of the metal shell with a working electrode port, connecting a platinum wire electrode with a counter electrode port, connecting a saturated calomel electrode with a reference electrode port to form a three-electrode system, and inserting the electrode with the insertion concentration of 10-3In mol/L tetrachloroauric acid solution, the step potential of the first step is-0.2V, the deposition time of the first step is 0.5s, the step potential of the second step is-2V, and the deposition time of the second step is 5 s; the number of deposition turns is 30 turns; the gold deposition curve is shown in figure 6. After deposition, taking out the device from the solution, then cleaning the device by using ultrapure water, and then drying the device for 5min at normal temperature; and then connecting the pins 2 and 3 of the metal shell with the working ports respectively, and repeating the steps to carry out multi-potential step electrodeposition. The SEM image of the resulting deposited gold is shown in fig. 7, from which it can be seen that: gold particles were deposited on the surface of the aluminum microelectrode array.
Example 3 preparation method of Polyacrylamide-dopamine modified microelectrode array
Weighing 0.37275g of KCl powder, putting the KCl powder into a 100mL volumetric flask, adding ultrapure water to dissolve the KCl powder, fixing the volume, and preparing a KCl aqueous solution with the concentration of 0.05 mol/L;
take 20mg of SiO2The powder was added to 50mL of an aqueous KCl solution and the SiO layer was sonicated2Dispersing the powder in KCl aqueous solution to obtain SiO2-a KCl dispersion;
0.3554g of acrylamide are weighed into a 50mL volumetric flask, 0.0076g of dopamine is weighed into a 50mL volumetric flask, and the prepared SiO is added into the volumetric flask2-KCl dispersion, to constant volume to obtain a concentration of 10-3Mixed solution of polyacrylamide and dopamine in mol/L。
Placing the interdigital aluminum microelectrode array in the central region of the inner bottom of the metal shell, connecting a pin 1 of the metal shell with a working electrode port, connecting a platinum wire electrode with a counter electrode port, and connecting a saturated calomel electrode with a reference electrode port to form a three-electrode system, and inserting the three-electrode system into the three-electrode system with the concentration of 10-3Opening an electrochemical workstation in a mixed solution of mol/L polyacrylamide and dopamine, starting a multi-potential step method, wherein the step potential of the first step is 2V, the deposition time of the first step is 1s, the step potential of the second step is-0.2V, and the deposition time of the second step is 0.2 s; the number of deposition turns was 30. The polyacrylamide-dopamine deposition curve is shown in figure 8. After the deposition, the metal case was taken out from the mixed solution, then washed with ultrapure water, and then dried at normal temperature for 5 min. And then taking the pin 2 and the pin 3 of the metal shell as working electrodes respectively, and repeating the steps to carry out electrodeposition. The SEM of the deposition effect of the obtained dopamine-acrylamide is shown in fig. 9, and it can be seen from fig. 9 that: a layer of polyacrylamide-dopamine mixed film is deposited on the surface of the aluminum microelectrode array.
Example 4 preparation of platinum modified microelectrode array
0.2589g of chloroplatinic acid was weighed into a 25mL volumetric flask, and diluted with a PBS buffer solution having a pH of 7 to a constant volume to prepare a chloroplatinic acid solution having a concentration of 0.02 mol/L.
Placing an interdigital aluminum microelectrode array in the central area of the inner bottom of a metal shell, opening an electrochemical workstation, starting a multi-potential step method, firstly connecting a pin 1 of the metal shell with a working electrode port, connecting a platinum wire electrode with a counter electrode port, and connecting a saturated calomel electrode with a reference electrode port to form a three-electrode system, inserting the three-electrode system into a chloroplatinic acid solution with the concentration of 0.02mol/L, wherein the step potential of the first step is-0.2V, the deposition time of the first step is 0.5s, the step potential of the second step is-2V, and the deposition time of the second step is 5 s; the number of deposition turns was 20, and the deposition curve is shown in FIG. 10. After the deposition, the metal case was taken out of the solution, then washed with ultrapure water, and then dried at normal temperature for 5 min. And then, respectively taking the pin 2 and the pin 3 of the metal shell as working electrodes, and repeating the steps to carry out multi-potential step electrodeposition. The SEM of the resulting platinum deposition effect is shown in FIG. 11.
Example 5 detection of dopamine
Preparation of first part dopamine sensor
Preparation of platinum deposition solution
0.0038g of dopamine is weighed to prepare 25mL of dopamine with the concentration of 10-3Taking 2.5mL of 10-concentration dopamine solution of mol/L- 3Weighing 0.2589g of chloroplatinic acid into a 25mL volumetric flask after the dopamine solution is in mol/L state, diluting the solution with a PBS buffer solution with the pH value of 7 to a constant volume, and obtaining a platinum deposition solution after the solution is completely dissolved;
preparation of platinum-dopamine modified aluminum microelectrode array
An interdigital aluminum microelectrode array is arranged in the central area of the inner bottom of a technical shell, a pin 2 of a metal shell is connected with a working port, a platinum wire electrode is connected with a counter electrode port, a saturated calomel electrode is connected with a reference electrode port to form a three-electrode system, and the three-electrode system is inserted into a platinum deposition solution and connected with an electrochemical workstation. Performing electrodeposition by using a multi-potential step method, wherein the step potential of the first step is-0.2V, the deposition time of the first step is 0.5s, the step potential of the second step is-2V, and the deposition time of the second step is 5 s; the number of deposition turns was 20. After deposition, the device was taken out of the solution, rinsed with ultrapure water, and then dried at normal temperature for 5min, and fig. 12 is a graph showing the effect of platinum-dopamine deposition, as can be seen by comparing fig. 11 and fig. 12: the polymerization effect of adding dopamine is better when the platinum is used for modifying the electrode.
Preparing gold deposition solution
0.0038g of dopamine is weighed to prepare 25mL of dopamine with the concentration of 10-3Taking 2.5mL of 10-concentration dopamine solution of mol/L- 3Weighing 0.0084g of tetrachloroauric acid into a 25mL volumetric flask after the dopamine solution is mol/L, diluting the tetrachloroauric acid into constant volume by using PBS buffer solution with the pH value of 7, and preparing the tetrachloroauric acid into 10-concentration dopamine solution after the tetrachloroauric acid is completely dissolved-3A tetrachloroauric acid solution in mol/L was used as the gold deposition solution.
Preparation of gold-dopamine modified aluminum microelectrode array
The interdigital aluminum microelectrode array is arranged in the central area of the inner bottom of the metal shell, a pin 1 of the metal shell is connected to a working electrode port, a platinum wire electrode is connected to a counter electrode port, a Saturated Calomel Electrode (SCE) is connected to a reference electrode port to form a three-electrode system, the three-electrode system is inserted into a gold deposition solution, and electrodeposition is carried out by adopting a multi-potential step method. The step potential of the first step is-0.2V, and the deposition time of the first step is 0.5 s; the step potential of the second step is-2V, and the deposition time of the second step is 5 s; the number of deposition turns was 30. After deposition, the device was taken out of the solution, rinsed with ultrapure water, and then dried at room temperature for 5 min.
Preparing polyacrylamide-dopamine modified solution
Weighing 0.37275g of KCl powder, putting the KCl powder into a 100mL volumetric flask, adding ultrapure water to dissolve the KCl powder, and performing constant volume to obtain a KCl aqueous solution with the concentration of 0.05 mol/L; take 20mg of SiO2Adding the powder into KCl aqueous solution, and ultrasonically treating SiO2Dispersing the powder in KCl aqueous solution to obtain SiO2-KCl dispersion. 0.3554g of acrylamide are weighed into a 50mL volumetric flask, 0.0076g of dopamine is weighed into a 50mL volumetric flask, and the prepared SiO is added into the volumetric flask2-KCl dispersion, to constant volume to obtain a concentration of 10-3And (3) storing the mixed solution of the polyacrylamide and the dopamine in a dark place after the mixed solution is completely dissolved, and using the mixed solution as a polyacrylamide-dopamine modified solution.
Preparation of polyacrylamide dopamine modified aluminum microelectrode array
The interdigital aluminum microelectrode array is arranged in the central area of a metal shell, a pin 3 of the metal shell is connected to a working electrode port, a platinum wire electrode is connected to a counter electrode port, a saturated calomel electrode is connected to a reference electrode port, a three-electrode system is formed, and the three-electrode system is inserted into a polyacrylamide-dopamine modified solution. Performing electrodeposition by adopting a multi-potential step method, wherein the step potential of the first step is 2V, and the deposition time of the first step is 1 s; the step potential of the second step is-0.2V, and the deposition time of the second step is 0.2 s; the number of deposited circles is 60 circles; and after deposition, taking the metal shell out of the polyacrylamide modified solution, washing with ultrapure water, and drying at normal temperature for 5min to obtain the polyacrylamide-dopamine modified aluminum microelectrode array.
The platinum-dopamine modified microelectrode array is used as a counter electrode, the gold-dopamine modified microelectrode array is used as a reference electrode, and the polyacrylamide-dopamine modified microelectrode array is used as a working electrode to form a three-electrode system. The three-electrode system is placed in the central area of the inner bottom of the metal shell, four pins of the metal shell are inserted into four small holes of the test box, and a metal column of the test box is correspondingly connected with a counter electrode end, a reference electrode end and a working port alligator clip of the electrochemical workstation. 8 mu.L of 0.1mol/L PBS buffer solution with pH of 6 is dripped into the chip area (the interdigital aluminum microelectrode array area) of the sensor. Starting an electrochemical workstation, and detecting by using a Differential Pulse Voltammetry (DPV), wherein the low potential is set to be-0.2V, the high potential is set to be 0.8V, and the amplitude is set to be 50mV, so that the DPV has a peak value at 0.2-0.3; indicating that dopamine was adsorbed on the working electrode.
Preparation of molecularly imprinted working electrode
And (3) carrying out desorption cleaning on dopamine:
mixing alcohol and water according to a volume ratio of 1: 1, mixing to obtain an ethanol water solution;
the platinum-dopamine modified microelectrode array is used as a counter electrode, the gold-dopamine modified microelectrode array is used as a reference electrode, and the polyacrylamide-dopamine decorated microelectrode array is used as a working electrode to form a three-electrode system. The three-electrode system is placed in the central area of the inner bottom of the metal shell, four pins of the metal shell are inserted into four small holes of the test box, and a metal column of the test box is correspondingly connected with a counter electrode end, a reference electrode end and a working port alligator clip of the electrochemical workstation; dropwise adding an ethanol aqueous solution on the interdigital aluminum microelectrode array, starting an electrochemical workstation, and using a time-current curve method, wherein the parameters of the time-current curve method comprise: and (3) washing with ultrapure water at a low potential of-0.2V for 50 circles, drying at room temperature for 10min, desorbing molecules of the substance to be detected, and preparing a molecularly imprinted sensing chip, namely preparing the interdigital microelectrode array electrochemical sensor for detecting dopamine.
Detection of a second fraction of different concentrations of dopamine
Preparing dopamine solutions with different concentrations
Weighing 0.0038g of dopamine, putting into 25mL of dopamine, dissolving the dopamine by using 0.1mol/L PBS buffer solution with the pH value of 7, fixing the volume, and preparing 10-3A dopamine mother liquor of mol/L;
measuring 100 mu L of mother solution of the substance to be detected, adding the mother solution into a 10mL volumetric flask, and diluting the mother solution into 10mL with PBS with corresponding pH value-5A mol/L solution of a substance to be detected;
measuring 300 mu L of mother solution of the substance to be detected, adding the mother solution into a 10mL volumetric flask, and diluting the mother solution into 3X 10 by PBS with corresponding pH value- 5A mol/L solution of a substance to be detected;
measuring 500 μ L of mother solution of the test substance, adding into a 10mL volumetric flask, diluting to 5 × 10 with PBS of corresponding pH value- 5A mol/L solution of a substance to be detected;
measuring 700. mu.L of mother solution of the test substance, adding the mother solution into a 10mL volumetric flask, and diluting the mother solution into 7X 10 by using PBS with corresponding pH value- 5A mol/L solution of a substance to be detected;
lysine was prepared at a concentration of 0.1. mu. mol/L for comparison;
PBS buffer at pH 7 was used as reference.
The platinum-dopamine modified microelectrode array is used as a counter electrode, the gold-dopamine modified microelectrode array is used as a reference electrode, and the dopamine imprinted polyacrylamide modified microelectrode array is used as a working electrode to form a three-electrode system. Inserted into the test box and connected to the corresponding three ports on the electrochemical workstation.
Dripping 8 mu L of dopamine mother liquor on the sensing chip; and starting the electrochemical workstation, and detecting by adopting a DPV method with the low potential set to be-0.2V and the high potential set to be 0.8V.
After the detection is finished, the sensor chip part is washed by ultrapure water, and the steps are repeated to test the next sample.
Fig. 13 is a DPV curve of a dopamine sample, a lysine sample, and a PBS buffer solution, as can be seen from fig. 13: the peak value of DPV is increasing with increasing dopamine concentration. The DPV of PBS and lysine is not peaked at 0.2-0.3, so that the sensor can be seen to respond differently to different concentrations of dopamine.
And establishing a linear regression equation between the peak current of the DPV curve and the concentration of the standard sample, and then detecting the actual sample. The regression equation is: y is 4.21659+0.4012x, where x is dopamine concentration and y is current.
The lower limit of the detection of the interdigital microelectrode array sensor on dopamine is 0.003 mu mol/L.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. An interdigital type microelectrode array electrochemical sensor is characterized by comprising an interdigital type aluminum microelectrode array, wherein the interdigital type aluminum microelectrode array is formed by combining three groups of aluminum microelectrode arrays in an interdigital mode and comprises a first aluminum microelectrode array, a second aluminum microelectrode array and a third aluminum microelectrode array; each group of aluminum microelectrode array is an electrode, and the three groups of aluminum microelectrode arrays form a three-electrode system comprising a working electrode, a counter electrode and a reference electrode.
2. The interdigitated microelectrode array electrochemical sensor of claim 1, wherein the first aluminum microelectrode array comprises a first backbone and a first comb array disposed on one side of the first backbone; the second aluminum microelectrode array comprises a second trunk and second comb-shaped arrays positioned on two sides of the second trunk, and the third aluminum microelectrode array comprises a third trunk and a third comb-shaped array positioned on one side of the third trunk; the second comb-shaped arrays on two sides of the second main stem are respectively interdigital to the first comb-shaped array on one side of the first main stem and the third comb-shaped array on one side of the third main stem.
3. The interdigitated microelectrode array electrochemical sensor of claim 1, wherein the counter electrode is a platinum-modified set of aluminum microelectrode arrays, the reference electrode is a gold-modified set of aluminum microelectrode arrays, and the working electrode is a analyte molecularly imprinted polymer-modified set of aluminum microelectrode arrays.
4. The interdigitated microelectrode array electrochemical sensor of claim 1, wherein the counter electrode is a platinum and deposition aid modified group of aluminum microelectrode arrays, the reference electrode is a gold and deposition aid modified group of aluminum microelectrode arrays, and the working electrode is a to-be-detected substance molecularly imprinted polymer modified group of aluminum microelectrode arrays.
5. The interdigitated microelectrode array electrochemical sensor of claim 3 or 4, wherein the substance to be measured is lysine, glucose or dopamine.
6. The interdigitated microelectrode array electrochemical sensor of claim 4, wherein the deposition aid is dopamine.
7. The interdigitated microelectrode array electrochemical sensor of claim 1 or 2 or 3 or 4 or 6, further comprising a metal shell, a flip-top lid mated to the metal shell; four pins are arranged at the outer bottom of the metal shell; the interdigital aluminum microelectrode array is arranged in the central area of the inner bottom of the metal shell; and three of the four pins are respectively connected with the three groups of aluminum microelectrode arrays of the interdigital aluminum microelectrode array through wires.
8. The preparation method of the interdigital microelectrode array electrochemical sensor of any one of claims 3 to 7, which comprises the following steps:
sputtering an aluminum film on a substrate, and photoetching the aluminum film to obtain an interdigital aluminum microelectrode array;
and respectively depositing a counter electrode material, a reference electrode material and a working electrode material on the three groups of aluminum microelectrode arrays of the interdigital aluminum microelectrode array to obtain the interdigital microelectrode array electrochemical sensor.
9. The application of the interdigitated microelectrode array electrochemical sensor of any one of claims 1 to 7 or the interdigitated microelectrode array electrochemical sensor obtained by the preparation method of claim 8 in the field of molecular detection.
10. The special test box for the interdigital microelectrode array electrochemical sensor, which is characterized by comprising a cuboid plastic body, wherein four small holes are drilled on one surface of the cuboid plastic body, and the positions and the sizes of the small holes correspond to the positions and the sizes of four pins of the interdigital microelectrode array electrochemical sensor respectively; copper sheets are padded at the bottoms of the holes of the small holes, and binding posts are led out by screws; the cuboid plastic body is made of polytetrafluoroethylene.
CN202011508466.4A 2020-12-18 2020-12-18 Interdigital microelectrode array electrochemical sensor, preparation method, application and special test box Pending CN112683975A (en)

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