CN113311049A - Preparation method and application of molecular imprinting screen printing electrochemical sensor of progesterone molecules - Google Patents
Preparation method and application of molecular imprinting screen printing electrochemical sensor of progesterone molecules Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a molecular imprinting screen printing electrochemical sensor of progesterone molecules, and belongs to the technical field of rapid detection. The invention uses progesterone as a template, adopts a surface imprinting technology to place a gold-containing electrode in electropolymerization liquid containing a monomer, a cross-linking agent, the template and an initiator for electropolymerization, and elutes template molecules to obtain the progesterone molecularly imprinted electrode. The molecularly imprinted electrode prepared by the invention can realize direct detection of progesterone molecules, has the advantages of sensitivity, rapidness, high specificity and the like, is low in price, and is suitable for detecting progesterone molecules on a substrate or on site.
Description
Technical Field
The invention relates to a preparation method and application of a molecular imprinting screen printing electrochemical sensor of progesterone molecules, belonging to the technical field of rapid detection.
Background
Progesterone (progestasterone), the primary progestin for women. Progesterone has important significance in maintaining pregnancy and enabling fertilized eggs to be implanted. The progesterone hormone is lower before ovulation of women, and obviously rises after the ovulation is completed, so that the stability of the uterus can be kept, the fallopian tube narrow part is kept in a relaxed state, the passing of pregnant eggs is facilitated, and the pregnancy can be normally carried out.
Progesterone detection methods are various, detection principles are different, and each method has own advantages and disadvantages, but due to the improvement of the sensitivity and accuracy requirements of modern food industry on the detection method, a plurality of methods are not suitable for detection. Therefore, the establishment of a sensitive, rapid, simple, convenient, high-specificity and economical detection method is an urgent need of production and operation enterprises, quality control personnel, import and export inspection traders and government management departments and a powerful guarantee of food and environmental safety.
At present, the common methods for detecting progesterone include high performance liquid chromatography, immunoassay, chemiluminescence, electrochemical methods and the like. However, these detection methods are often time-consuming and labor-intensive and require high detection costs.
The invention is characterized in that the molecular imprinting is electroplated on a screen printing electrode, the molecular imprinting is also called as an artificial antibody, the requirement on the environment is not high, a special preservation mode is not needed, in addition, the invention has better identification capability on progesterone molecules, and the requirement on specificity detection is achieved. In order to realize the molecular imprinting of the progesterone molecule, we made some adjustments on the basis of considering the properties of the progesterone molecule itself on the basis of the similar prior inventions: the combination of the surface of the electrode and the gold nano-particles adopts an electroplating mode, but not a direct dripping and drying mode, because the experiment shows that the dripping and coating combined gold nano-particles are not uniform by an electroplating method. Secondly, when preparing a solution with a standard concentration, ethanol is used as a solvent, the solubility of the progesterone in water is not high, acetonitrile and methanol are also used as solvents for determination according to the chemical structure of the progesterone, and the fact that although the capability of dissolving the progesterone by the acetonitrile and the methanol is better than that of the ethanol, the acetonitrile and the methanol have certain influence on a copolymerization membrane adsorbed on a screen printing electrode is found, and the ethanol is finally selected as the solvent of the progesterone by integrating various factors. And thirdly, because of certain difference between the electrodes, the method is a standard curve between the concentration of the substance to be measured in the constructed solution of the substance to be measured and the peak current difference (the current value before adsorption minus the current value after adsorption) when constructing the standard curve.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a molecular imprinting screen printing electrochemical sensor for quickly detecting progesterone.
The invention aims to provide a molecularly imprinted electrochemical sensor for rapidly detecting progesterone, which is formed by horizontally inserting a disposable molecularly imprinted screen-printed electrode serving as a working click into a clamping groove of an electrochemical workstation of a multi-channel potentiostat; the multi-channel potentiostat electrochemical workstation comprises 1-8 sample measurement channels;
the molecular imprinting screen printing electrode comprises an electrode substrate, a wiring terminal, an electrode connecting wire, a working electrode, a counter electrode and an insulating layer; and a progesterone molecularly imprinted polymer film is electroplated on the surface of the working electrode.
In one embodiment of the invention, the molecular imprinting screen printing electrode, the electrode substrate is a disposable consumption substrate, the working electrode, the counter electrode and the reference electrode are led out by an electrode connecting wire to form a convex three-wire socket which can be inserted into an electrochemical detector for detecting and reading.
In one embodiment of the invention, the molecularly imprinted screen printed electrode has an electrode substrate printed with a connecting terminal, one electrode substrate with an electrode connecting line integrally connected with a working electrode and a connecting terminal, and the other electrode substrate with an electrode connecting line integrally connected with a counter electrode, wherein the two electrode connecting lines are parallel to each other, the electrode connecting line is arranged in the middle of the electrode substrate, and the surface of the electrode connecting line is coated with a layer of PVC insulator.
In one embodiment of the invention, the molecularly imprinted screen printing electrode has a round block-shaped working electrode, a semicircular ring-shaped counter electrode concentric with and separated from the working electrode, and a polymerized progesterone molecularly imprinted membrane is electroplated on the surface of the working electrode.
In one embodiment of the present invention, the process of electroplating the progesterone molecularly imprinted polymer membrane comprises:
dripping gold nano cross (the gold nano layer can enhance the contact specific surface area of the electropolymerized molecular imprinting polymer film after the gold nano layer is enhanced, and increase the electron transfer rate, thereby increasing the sensitivity), electroplating, drying, modifying p-mercaptoaniline through gold mercapto bond, immersing 1 mmol.L of p-mercaptoaniline-1And incubating at room temperature for 4h in a progesterone solution, then placing in an electropolymerization solution, electroplating and polymerizing, eluting template molecules, and electroplating a molecularly imprinted polymer film on the surface of the working electrode to obtain the molecularly imprinted screen printing electrode.
In one embodiment of the present invention, the dropping of the gold nano-cross comprises: and (4) dripping the prepared gold nano cross solution on the surface of the working electrode, and performing electroplating deposition to complete the coverage of the gold nano cross.
In one embodiment of the present invention, the gold nanoparticle cross solution is prepared by the following process: 5ml of 0.5 mmol. multidot.L-1HAuCl4With 5ml of 0.2 mol. L-1CTAB was mixed, 400. mu.l of ultrapure water was added, and 0.6ml of 0.01 mol. L was added-1NaBH4(fresh preparation), stirring for 2min, and standing for 30min to obtain gold seeds. Dissolving 0.9g CTAB and 0.08g sodium salicylate with 25ml ultrapure water at 50 deg.C, cooling to 30 deg.C, adding 0.6ml 4 mmol.L-1AgNO31028.8 μ L of 24.28 mmol. multidot.L-1And 23.9712ml of ultrapure water, stirred for 15min, and added with 700. mu.l of 0.1 mol. L-1And stirring vigorously for 30s until the solution is colorless. Finally, adding gold seeds into the solution, stirring for 30s, and standing and growing for 12h at 30 ℃.
In one embodiment of the present invention, the electropolymerization liquid includes: the concentration range of the p-mercaptoaniline is 5-15mmol/L, the concentration range of the tetrabutylammonium perchlorate is 30-80mol/L, the concentration range of the 4, 4' -bipyridyl is 5-15mol/L, and the concentration range of the perchloric acid is 0.2-0.6 g/L.
In one embodiment of the present invention, the electropolymerization liquid specifically contains 10 mmol. L-1P-mercaptoaniline, 50 mmol.L-1 tetrabutylammonium perchlorate, 1 mmol.L-1 progesterone and 0.4g/L perchloric acid.
In one embodiment of the present invention, the specific conditions for the electroplating polymerization are: the electropolymerization voltage is-0.3V-1.2V, the scanning speed is 50mv/s, and the optimal number of scanning circles is 10 circles.
In one embodiment of the invention, the template molecule is eluted by immersing the electrode in a solution containing HCl-ethanol (4: 1, v/v) for 3min, and then rinsing the working electrode with ultrapure water.
The second purpose of the invention is to provide the application of the molecular imprinting electrochemical sensor in the progesterone detection.
In one embodiment of the invention, the application is that firstly, the conductive liquid is dripped on a working electrode of a progesterone molecular engram polymer membrane plated on the surface of the electrochemical sensor, the voltage is set, and the peak current value I when the progesterone molecular engram polymer membrane is not adsorbed is measured0(ii) a Dropwise adding a substance to be measured with a known concentration of standard molecules onto the working electrode, standing for adsorption, dropwise adding a conductive liquid after adsorption is completed, setting voltage, and measuring a peak current value I; calculating to obtain a current signal difference I-I0And constructing a linear relation between the concentration and the current signal difference value to obtain a detection model.
In one embodiment of the invention, an unknown sample solution to be detected is dripped on the surface of a molecular imprinting screen printing electrode, the molecular imprinting screen printing electrode is adsorbed for a certain time, then the disposable molecular imprinting screen printing electrode is horizontally inserted into a clamping groove of an electrochemical workstation of a multi-channel potentiostat, an electrolyte is dripped, and reading is detected; the concentration of progesterone was then calculated using the above described assay model.
In one embodiment of the invention, the electrochemical sensor is a multi-channel potentiostat electrochemical workstation, and is provided with a computer display screen, the detector is arranged under a certain voltage, electrons emitted by the counter electrode flow through the conductive liquid, and the current value formed when the electrons flow back to the workstation from the working electrode is recorded, and the concentration of the target substance in the sample to be detected is finally displayed on the computer display screen according to the conversion between the magnitude of the generated current and the concentration of the target substance in the standard sample; the multiple channels are 1-8 sample measurement channels.
In one embodiment of the present invention, the medium of the sample solution to be tested is ethanol.
In an embodiment of the present invention, the volume of the sample solution to be detected, which is dropped onto the surface of the molecularly imprinted screen-printed electrode during the adsorption process, is: 10-60 mu L.
In one embodiment of the present invention, the volume of the sample solution to be tested, which is dropped onto the surface of the molecularly imprinted screen-printed electrode during the adsorption process, is 40 μ L in an optimized embodiment of the present invention.
In one embodiment of the invention, the time for standing and adsorbing the to-be-detected sample solution is 50-600 s after the solution is dripped on the surface of the molecularly imprinted screen printing electrode; preferably 180 s.
In one embodiment of the present invention, the voltage is set in a range of-0.2V to 0.6V; preferably-0.2V to 0.4V.
In an embodiment of the invention, the standard molecularly imprinted screen-printed electrode (the standard before adsorption and the standard after adsorption) is inserted first, the detection result of the portable detector is corrected according to the standard curve of the peak current difference and the progesterone sample concentration, and then the molecularly imprinted screen-printed electrode for completing the adsorption of the sample to be detected is inserted.
In one embodiment of the invention, the application is that more than two concentrations of standard molecularly imprinted screen-printed electrodes (the electrode corresponding to each concentration comprises a standard before adsorption and a standard after adsorption) are inserted to correct the detector.
In one embodiment of the present invention, the standard curve is prepared by dropping an electric conducting solution on the eluted molecularly imprinted screen-printed electrode, measuring a peak current value, preparing ethanol solutions containing different measured substances with known concentrations, dropping the ethanol solutions into the molecularly imprinted screen-printed electrode of the measured substance (the measured substance with the standard concentration is used for setting the standard curve), washing after adsorbing for a certain time, dropping the electric conducting solution, detecting by a portable detector, recording data, and calculating the standard curve between the substance concentration in the measured substance solution and the peak current difference (the current value before adsorption minus the current value after adsorption). And (4) carrying out calibration according to the standard curve, and carrying out technical reference inside the system when the calibration is used for detecting and analyzing the actual sample.
In one embodiment of the invention, the use is for the detection of progesterone. The molecular imprinting screen printing electrode is a progesterone molecular imprinting screen printing electrode, and y is 0.53343lg +9.233 (R)20.95989) detection limit of 10- 14mol/L。
The invention has the beneficial effects that:
(1) the electrochemical work station of the multi-channel potentiometer mainly has three characteristics of rapidness, high efficiency and sensitivity.
(2) The surface of the screen printing electrode is electroplated with gold nano-crosses, so that the contact specific surface area of the molecularly imprinted polymeric membrane which is then electroplated and polymerized is enhanced, the electron transfer rate is increased, the sensitivity is increased, and the response signal of the electrode is enhanced.
(3) The molecular imprinting polymer membrane is used as an identification target, has strong detection specificity, is not influenced by the color and the turbidity of the sample, and has the advantages that the sample can be processed without complexity and is not required to be separated. By combining an electrochemical analysis method capable of quickly and sensitively detecting and the low cost and high performance of the screen printing electrode, the progesterone molecules in the sample can be quickly and conveniently detected (after the extracting solution of the sample to be detected is obtained, the detection can be completed within a few minutes, the peak current value before adsorption can be detected and recorded in advance, and thus, only the peak current value after adsorption needs to be obtained again).
(4) The detector of the invention is a rapid detection product which can really solve the market demand and meet the detection demands of the departments of industry and commerce, quality inspection institutions, scientific research colleges and the like, can be used for production and operation enterprises, quality control personnel, import and export inspection traders, government management departments, hospitals and even individual families, and is suitable for the fields of food industry, feed industry, environmental protection, medical drug screening, biochemistry and the like.
Drawings
FIG. 1 is a schematic diagram of preparation of a progesterone molecularly imprinted screen-printed electrode sheet;
FIG. 2 is a structural diagram of a progesterone molecular imprinting electrochemical detector;
FIG. 3 is a standard curve detection of a portable progesterone molecular imprinting electrochemical detector;
FIG. 4 is a cyclic voltammogram of the front and rear electrodes to which gold nanoprosses were added.
Detailed Description
In order to clearly understand the technical contents of the present invention, the following examples are given in detail for the purpose of better understanding the contents of the present invention and are not intended to limit the scope of the present invention.
Example 1 preparation of progesterone molecularly imprinted screen printed electrode
The preparation schematic diagram of the progesterone molecular imprinting screen printing electrode plate is shown in figure 1. The preparation method comprises the following steps:
(1) electroplating and depositing gold nano cross on the surface of a working screen printing electrode, wherein the electroplating method comprises the following steps: and (4) dripping the prepared gold nano cross solution on the surface of the working electrode, and performing electroplating deposition.
(2) P-mercaptoaniline is modified through gold mercapto bond, and the modification method comprises the following steps: dipping the screen printing electrode coated with gold nano particles into 50 mmol.L-1Soaking in mercaptoaniline ethanol solution at room temperature for 24h, then thoroughly washing with water to remove non-adsorbed mercaptoaniline, and drying with infrared lamp for use;
(3) then dipping the screen printing electrode modified with p-mercaptoaniline into 1 mmol.L-1Incubating the progesterone solution for 4 hours at room temperature, washing the progesterone solution by using ultrapure water, and then drying the progesterone solution by using an infrared lamp for later use; then, the screen-printed electrode after electrostatic adsorption was immersed in 10mL of a solution containing 10 mmol. L-1P-mercaptoaniline, 50 mmol. L-1Tetrabutylammonium perchlorate, 1 mmol. L-1Progesterone and 0.4 g.L-1Perchloric acid, adopting cyclic voltammetry for scanning, and electropolymerization voltage is as follows: -0.3V-1.2V, scan rate: 50mv/s, number of scan cycles: 10;
(4) and finally, eluting template molecules, soaking the screen printing electrode of the electro-polymerization progesterone molecularly imprinted membrane in HCl/ethanol solution (4: 1, v/v) for 3min, and then leaching the screen printing electrode with ultrapure water to finish the preparation of the screen printing electrode of the progesterone molecularly imprinted membrane.
Example 2 application of progesterone molecularly imprinted screen printed electrodes
The sample testing procedure was as follows:
firstly, a standard (progesterone with known concentration) molecular imprinting screen printing electrode is inserted into a clamping groove of an electrochemical workstation of a multi-channel potentiometer, and a detection result is corrected. Then preparing the purified progesterone sample into ethanol solution, dripping 20 mu L of progesterone sample aqueous solution on the surface of a screen printing electrode of the prepared progesterone molecular imprinting membrane, and standing for adsorption time: 180s, washing after the adsorption is finished, then dropwise adding the electric conduction liquid, and configuring the electric conduction liquid: 2.5 mmol. L-1[Fe(CN)6]3-/4-And 0.1 mol. L-1KCl solution, voltage setting range: -0.2V to 0.4V, recording the current peak value in scanning, calculating according to the standard curve between the progesterone concentration and the current peak value arranged in the progesterone special electrochemical sensor, and finally displaying the measured progesterone concentration in the sample on a computer display screen.
The structure diagram of the progesterone molecular imprinting electrochemical detector is shown in fig. 2, and the structure is as follows:
the molecular imprinting screen printing electrode comprises an electrode substrate, a wiring terminal, an electrode connecting wire, a working electrode, a counter electrode and an insulating layer; the surface of the working electrode is electroplated with a molecularly imprinted polymer film; the electrode substrate is a disposable consumption substrate, the working electrode, the counter electrode and the reference electrode are led out by an electrode connecting line to form a convex three-wire socket which can be inserted into a clamping groove of an electrochemical workstation of the multichannel potentiometer to detect and read. The electrode substrate is printed with a connecting terminal, an electrode matrix and a connecting terminal, wherein the electrode matrix and the connecting terminal are connected into a whole, the electrode matrix and the counter electrode are connected into a whole, the two electrode connecting lines are parallel to each other, the electrode connecting line is arranged in the middle of the electrode matrix, and the surface of the electrode matrix is coated with a layer of PVC insulator. The working electrode is in a round block shape, the counter electrode is in a semicircular annular block shape concentric with and separated from the working electrode, and the surface of the working electrode is electroplated with the polymerized progesterone molecularly imprinted membrane.
The electrochemical sensor is an electrochemical workstation with set voltage, is provided with a computer display screen and is used for recording the current value formed when electrons flowing out of the counter electrode flow through a sample or an electric conducting liquid and then flow back to the workstation from the working electrode. The current is recorded by an electrochemical detector, calculated by a standard curve prepared by a progesterone molecular imprinting screen printing electrode with standard concentration, and displayed on a computer display screen in a concentration form.
Example 3 application of progesterone molecularly imprinted screen printed electrodes
In one portable detector of the invention, which is a progesterone-specific portable detector, a standard curve between progesterone concentration and peak current has been built into the detector program.
The standard curve drawing method comprises the following steps: preparation of different known concentrations (concentration range: 1X 10)-14～1×10-8mol·L-1) The progesterone molecular imprinting screen printing electrode is inserted into a detector, a current peak value formed when electrons flow from a counter electrode, pass through an electric conduction liquid and then flow back to a workstation from a working electrode is detected, the progesterone concentration is taken as a horizontal coordinate, and a peak current difference value is taken as a vertical coordinate, so that a standard curve is obtained, as shown in fig. 3. The standard curve equation is obtained as y-0.53343 lg +9.233 (R)20.95989) detection limit of 10-14mol/L。
And (4) embedding the obtained standard curve in a detector through a computer program to obtain the special portable detector for the progesterone.
When a sample to be detected is detected, more than 2 progesterone standard substance molecularly imprinted screen-printed electrodes are used for correction, and then a sample solution to be detected is detected. The portable detector can finally and directly display the concentration of the progesterone in the sample to be detected on a computer display screen of the detector according to an internally set standard curve.
Example 4 Standard Curve
In one detector of the present invention, the standard curve is not built into the detector program. For different measured substances, an operator can prepare molecularly imprinted screen printed electrodes (including electrodes before adsorption and electrodes after adsorption) of the measured substances with different known concentrations, insert the electrodes into a detector and input the concentrations into the detector on an operation interface of the detector respectively, a detector system can calculate to obtain a standard curve of the magnitude of a current value difference and the concentration of the substances according to the magnitude of the measured current value difference and received concentration information, then the operator detects the sample to be detected, and the inside of the system can directly display the concentration of the target substances in the sample to be detected according to the measured current value difference and the calculated standard curve.
Example 5 optimization of assay conditions
1) Optimizing standing adsorption time:
referring to example 2, the standing adsorption time was changed to 80s and 300s, and the other conditions were not changed to obtain the detection results, thereby preparing a calibration curve. As a result, it was found that: when the adsorption time is 80s, the peak current value corresponding to each concentration standard sample is generally low, which indicates that the adsorption is insufficient and is not beneficial to final reading; when the adsorption time is 300s, the peak current value corresponding to each concentration standard sample is basically the same as that when the adsorption time is 180s, but the dropwise added standard sample solution is observed to be obviously reduced, which indicates that the solution is volatilized, so in summary, the standing adsorption time is selected to be 180 s.
2) Optimization of the amount of sample solution:
referring to example 2, the amount of progesterone sample solution was changed to 10L and 60 μ L, and other conditions were not changed to obtain the test results, and a standard curve was prepared. As a result, it was found that: when the amount is 10 μ L, it can be observed that the progesterone sample solution is significantly reduced due to volatilization, and progesterone molecules have certain volatility, so that a part of progesterone molecules may not be adsorbed, which makes the peak current detection value lower than its true value; when the dosage is 60 muL, the progesterone sample solution is easy to flow away from the surface of the working electrode during dripping, and the absorption is insufficient, so that the peak current detection value is lower than the true value. Therefore, we chose the amount of progesterone sample solution to be 20 μ L.
3) Optimizing the detection voltage:
referring to example 2, the voltage range was expanded to-0.6V to 0.6V, and the other conditions were not changed, and the results were measured to obtain a calibration curve. As a result, it was found that: within the voltage range of-0.6V to-0.2V and 0.4V to 0.6V, the DPV curve of the electrode has more mixed peaks and small data significance, within the range of-0.2V to 0.6V, the DPV curve of the electrode is smooth, the reading of the peak current value is accurate, and the detection time is saved. Therefore, we select the detection voltage range to be-0.2V-0.6V.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A molecular imprinting electrochemical sensor for rapidly detecting progesterone is characterized in that a molecular imprinting screen printing electrode is horizontally inserted into a clamping groove of an electrochemical workstation of a multi-channel potentiostat to form the molecular imprinting electrochemical sensor; the multi-channel potentiostat electrochemical workstation comprises 1-8 sample measurement channels;
the molecular imprinting screen printing electrode comprises an electrode substrate, a wiring terminal, an electrode connecting wire, a working electrode, a counter electrode and an insulating layer; and a progesterone molecularly imprinted polymer film is electroplated on the surface of the working electrode.
2. The molecularly imprinted electrochemical sensor according to claim 1, wherein the process of electroplating the progesterone molecularly imprinted polymer membrane comprises:
dropwise adding gold nano crosses (the gold nano layer can enhance the contact specific surface area of a later electropolymerized molecular imprinting polymer film and increase the electron transfer rate so as to increase the sensitivity) on the surface of a working electrode of a common screen printing electrode, electroplating, drying, modifying p-mercaptoaniline through gold mercapto bonds, immersing the p-mercaptoaniline in a progesterone solution, incubating at room temperature, then placing in an electropolymerization solution, electroplating and polymerizing, eluting template molecules, and electroplating a molecular imprinting polymer film on the surface of the working electrode to obtain the molecular imprinting screen printing electrode.
3. The molecularly imprinted electrochemical sensor according to claim 2, wherein the dropping of the gold nano cross comprises: and (4) dripping the prepared gold nano cross solution on the surface of the working electrode, and performing electroplating deposition to complete the coverage of the gold nano cross.
4. The molecularly imprinted electrochemical sensor of claim 2, wherein the electropolymerization fluid comprises: the concentration range of the p-mercaptoaniline is 5-15mmol/L, the concentration range of the tetrabutylammonium perchlorate is 30-80mol/L, the concentration range of the 4, 4' -bipyridyl is 5-15mol/L, and the concentration range of the perchloric acid is 0.2-0.6 g/L.
5. The molecularly imprinted electrochemical sensor of claim 2, wherein the conditions of the electroplating polymerization are: the electropolymerization voltage is-0.3V-1.2V, the scanning speed is 50mv/s, and the optimal number of scanning circles is 10 circles.
6. Use of a molecularly imprinted electrochemical sensor according to any of claims 1 to 5 for the detection of progesterone.
7. A method for detecting progesterone content is characterized in that an electric conduction liquid is dripped on a working electrode of a surface-plated progesterone molecularly imprinted polymer membrane in a molecularly imprinted electrochemical sensor according to any one of claims 1 to 5, voltage is set, and the peak current value I when the progesterone is not adsorbed is measured0(ii) a Dropwise adding a solution of a to-be-detected substance with a known concentration and a standard molecular concentration onto a working electrode, standing for adsorption, dropwise adding a conductive liquid after adsorption is completed, setting a voltage, and measuring a peak current value I; calculating to obtain a current signal difference I-I0And constructing a linear relation between the concentration and the current signal difference value to obtain a detection model.
8. The method of claim 7, wherein the volume of the sample solution to be measured dropped on the surface of the working electrode is 10 μ L to 60 μ L.
9. The method of claim 7, wherein the standing adsorption time is 50s to 600 s.
10. The method according to claim 7, wherein the voltage is set in a range of-0.2V to 0.6V; preferably-0.2V to 0.4V.
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