CN115791916A - Probe type electrochemical detection device and preparation method and application thereof - Google Patents
Probe type electrochemical detection device and preparation method and application thereof Download PDFInfo
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- APSNPMVGBGZYAJ-GLOOOPAXSA-N clematine Natural products COc1cc(ccc1O)[C@@H]2CC(=O)c3c(O)cc(O[C@@H]4O[C@H](CO[C@H]5O[C@@H](C)[C@H](O)[C@@H](O)[C@H]5O)[C@@H](O)[C@H](O)[C@H]4O)cc3O2 APSNPMVGBGZYAJ-GLOOOPAXSA-N 0.000 claims abstract description 42
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Abstract
The invention discloses a probe type electrochemical detection device and a preparation method and application thereof. The probe type electrochemical detection device comprises a probe type electrochemical sensor and a matched micro reaction tank. The probe type electrochemical detection device has the characteristics of high integration level, small volume, low cost, strong practicability and the like, and has the advantages of few detection samples, simple detection operation process, quick response, high sensitivity and the like when in detection and use, and can realize quick and accurate detection. The preparation method can realize the high-efficiency assembly of the probe-type electrochemical detection device, and the performance of the prepared and produced probe-type electrochemical detection device can be measured by adopting common electrochemical indicators such as potassium ferricyanide and the like. The probe type electrochemical detection device has the advantages of high sensitive response, wide linear range, high recovery rate, low relative deviation and the like on the hesperidin in the solution, and can realize the rapid detection on the hesperidin in the solution.
Description
Technical Field
The invention relates to the technical field of electrochemical analysis and detection, in particular to a probe type electrochemical detection device and a preparation method and application thereof.
Background
With the increasing health consciousness of people, the requirements of people on the quality of food are higher and higher. Natural antioxidants are a class of physiologically active substances widely found in agricultural and sideline products such as vegetables, fruits and tea leaves, including flavonoids. Researches show that the natural antioxidant has important functions in preventing cancers and cardiovascular and cerebrovascular diseases, delaying aging, promoting metabolism of human bodies and the like. Thus, the content of natural antioxidants often determines the quality of these agricultural and sideline products and their processed products.
The traditional analysis and detection methods for the content of the natural antioxidant comprise an ultraviolet-visible spectrophotometry, a high performance liquid chromatography, a gas chromatography and the like, the traditional analysis and detection methods for the content of the natural antioxidant generally have the problems of complicated sample treatment, complicated instruments and equipment, long analysis and detection time consumption, high cost and the like, and are particularly not suitable for the rapid determination of the content of the antioxidant in food and agricultural products in daily life.
In recent years, electrochemical-based analysis techniques have attracted much attention, but at present, there is no conventional electrochemical device suitable for rapid detection of natural antioxidants including flavonoids, and the conventional electrochemical device has low detection accuracy, and meanwhile, the conventional electrochemical device has a complicated preparation method and is generally expensive, which limits its wide use in practical production.
Disclosure of Invention
The invention aims to solve the problems of low traditional detection efficiency, low electrochemical detection precision, high cost and the like of natural antioxidants including flavonoids and the like in the prior art, and provides a probe-type electrochemical detection device.
Another object of the present invention is to provide a method for preparing the probe-type electrochemical detection device, which can be used for large-scale preparation and production of the probe-type electrochemical detection device.
The invention also aims to provide application of the probe type electrochemical detection device, and particularly can be applied to rapid detection of the concentration of hesperidin in a solution.
The purpose of the invention is realized by the following technical scheme.
A probe type electrochemical detection device comprises a probe type electrochemical sensor and a micro reaction tank;
the probe type electrochemical sensor comprises a pencil lead working electrode, an auxiliary electrode and a reference electrode; the pencil lead working electrode comprises a pencil lead which is packaged in an insulating tube, two ends of the pencil lead are exposed out of the insulating tube, and the auxiliary electrode and the reference electrode are formed outside the insulating tube;
one end of the probe type electrochemical sensor is an interface end, and the other end of the probe type electrochemical sensor is a detection end; the pencil lead working electrode, the auxiliary electrode and the reference electrode are respectively connected with a conductive patch which is electrically connected with an electrochemical workstation, corresponding to the interface end of the probe type electrochemical sensor; when the probe type electrochemical sensor is used, the detection end of the probe type electrochemical sensor is inserted into the micro reaction tank.
In a preferred embodiment, the space between the pencil lead and the insulating tube is filled with epoxy resin and cured.
In a preferred embodiment, the auxiliary electrode and the reference electrode are conductive silver paste coated on the outer wall of the insulating tube and dried.
In a preferred embodiment, the insulating tube comprises a plastic tube or a glass tube, and the insulating tube comprises a capillary tube.
In a preferred embodiment, the probe-type electrochemical detection device of any one of the above embodiments, the micro reaction cell is configured with a cell cover, and the cell cover has an electrode receptacle and a sample application hole; when the probe type electrochemical sensor is used, the detection end of the probe type electrochemical sensor extends into the micro reaction tank from the electrode jack.
A preparation method of a probe type electrochemical detection device comprises the following steps:
s1, a pencil lead is inserted into an insulating tube, wherein the pencil lead is exposed out of two ends of the insulating tube, and a gap between the pencil lead and the insulating tube is filled and solidified to obtain a pencil lead working electrode;
s2, coating the auxiliary electrode conductive paste and the reference electrode conductive paste on two sides of the outer wall of the insulating tube, and drying to obtain an auxiliary electrode and a reference electrode, wherein the auxiliary electrode and the reference electrode are not connected with each other;
s3, connecting conductive patches to one ends of the pencil lead working electrode, the auxiliary electrode and the reference electrode to obtain the probe type electrochemical sensor;
and S4, adopting an insulating container as a micro reaction tank, and enabling one end of the probe-type electrochemical sensor, which is not provided with the conductive patch, to be inserted into the micro reaction tank in a matched manner, so as to obtain the probe-type electrochemical detection device.
In a preferred embodiment, the auxiliary electrode conductive paste and the reference electrode conductive paste are conductive silver pastes, and the drying is performed at 80-120 ℃ for 1-5 hours.
In a preferred embodiment, the insulating container may be a plastic round tube.
In a preferred embodiment, in the method for manufacturing a probe-type electrochemical detection device according to any one of the above embodiments, a cell cover is disposed on the micro reaction cell, and the cell cover has an electrode receptacle and a sample application hole; when the probe type electrochemical sensor is used, one end of the probe type electrochemical sensor, which is not provided with the conductive patch, is inserted into the micro reaction cell from the electrode jack.
The probe type electrochemical detection device of any one of the above applications, including the applications in food detection and agricultural product detection.
The probe-type electrochemical detection device is applied to rapid detection of the concentration of hesperidin, specifically, an electrocatalytic oxidation reaction of hesperidin is carried out on a pencil lead working electrode of the probe-type electrochemical detection device to generate a catalytic current, a substance to be detected can be judged to be hesperidin according to a voltage position when the catalytic current is generated, and the concentration of hesperidin can be obtained through calculation according to the magnitude of the generated catalytic current. The application of the method in rapid detection of the hesperidin concentration comprises the following steps:
s1, inserting a detection end of the probe-type electrochemical sensor into the micro reaction tank, assembling the probe-type electrochemical detection device, and connecting the probe-type electrochemical sensor with an electrochemical workstation;
s2, adding a buffer solution into a micro reaction cell of the probe type electrochemical detection device, and measuring and obtaining a voltammetry curve of a blank solution;
s3, adding hesperidin solutions with different concentrations into a micro reaction tank of the probe type electrochemical detection device, and measuring and obtaining voltammetry curves of the hesperidin solutions with different concentrations;
s4, determining catalytic current values corresponding to the voltammetry curves according to the corresponding voltammetry curves of the hesperidin solutions with different concentrations, further determining the relationship between the hesperidin concentration and the catalytic current, and making a concentration-current curve;
s5, performing linear fitting on the obtained concentration-current curve to obtain a fitting curve;
s6, adding target hesperidin solutions with the same concentration into at least three probe-type electrochemical detection devices respectively, obtaining corresponding hesperidin concentrations by contrasting the fitting curve according to the peak current value of the measured target hesperidin solution, calculating an average value, and determining the average value as the detection concentration of the target hesperidin solution.
In a preferred embodiment, the buffer solution comprises a phosphate buffer solution having a pH of 6.9.
In a particularly preferred embodiment, the concentration of the phosphate buffer solution at pH 6.9 is 0.2M (M = mol/dm) 3 ) The addition amount is 1000-1500 μ L (L = dm) 3 )。
In a preferred embodiment, the voltammogram comprises a cyclic voltammogram or a linear voltammogram measured over a potential range of 0.6-0.1V at a scan rate of 0.01V/s.
In a preferred embodiment, in S6, after at least three hesperidin concentrations respectively corresponding to the probe-type electrochemical detection apparatus are obtained, the recovery rate and the relative standard deviation are calculated, and the accuracy and the repeatability of the probe-type electrochemical detection apparatus are verified.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the probe type electrochemical detection device has the characteristics of high integration level, small volume, low cost, strong practicability and the like, needs few detection samples during detection and use, is simple in detection operation process, quick in response and high in sensitivity, can realize quick and accurate detection, can be used in the quality control fields of food detection, agricultural product detection and the like, is particularly suitable for quick evaluation of food, medicine quality and agricultural product quality in daily life, and has wide application prospect.
The preparation method can realize the efficient assembly of the probe-type electrochemical detection device, and the performance of the prepared and produced probe-type electrochemical detection device can be measured by adopting common electrochemical indicators such as potassium ferricyanide, so that the large-scale efficient production of the probe-type electrochemical detection device can be realized, and the wide application of the probe-type electrochemical detection device is facilitated.
The probe type electrochemical detection device has high sensitive response (the sensitivity reaches 0.0021A/M) to hesperidin in solution and wide linear range (the linear value is 5 multiplied by 10) -7 -1×10 -4 M), high recovery rate (the recovery rate reaches 102-109%, namely, the corresponding accuracy is high), low relative deviation (the relative standard deviation is +/-3%, namely, the repeatability is high), and the like, and can realize the rapid detection of the hesperidin in the solution.
Drawings
FIG. 1 is a schematic structural diagram of a probe-type electrochemical detection device according to one embodiment of the present invention;
FIG. 2 is a plot of cyclic voltammetry for potassium ferricyanide/potassium ferrocyanide prepared in example two;
FIG. 3 is a graph of a linear voltammetry curve for detecting a hesperidin solution in the third embodiment;
FIG. 4 is a graph showing the relationship between the concentration and the current of the hesperidin solution detected in the third embodiment;
FIG. 5 is a graph showing the detection of hesperidin solution in the third embodiment.
The attached drawings are marked as follows: 1-pencil lead working electrode, 101-pencil lead, 102-insulating tube, 2-auxiliary electrode, 3-reference electrode, 4-micro reaction cell, 5-cell cover, 501-electrode jack, 502-sample adding hole and 6-conductive patch.
Detailed Description
The technical solution of the present invention is further described in detail with reference to specific examples, but the scope and implementation of the present invention are not limited thereto. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It is obvious that the drawings in the following description are only a part of the embodiments of the invention, and that other drawings can be derived from these drawings by a person skilled in the art without inventive effort.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the reagents, equipment and methods employed herein are those conventionally available and commercially available in the art. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is standard in the art to which the claimed subject matter belongs. In case there are multiple definitions for a term, the definitions herein control.
Unless otherwise indicated, the present invention employs standard nomenclature for analytical chemistry, organic synthetic chemistry, and optics, and standard laboratory procedures and techniques.
It should be understood that as used herein, singular forms, such as "a", "an", include plural references unless the context clearly dictates otherwise. Furthermore, the terms "comprising," "including," and "having" are intended to be open-ended, meaning that they do not exclude other aspects, and are not intended to be inclusive in nature. In other words, the term also includes "consisting essentially of or" consisting of 823030A ". In addition, "and a combination thereof" in the specification refers to any combination of all items listed.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
Example one
Referring to fig. 1, the probe-type electrochemical detection apparatus of the present invention includes a probe-type electrochemical sensor and a micro-reaction cell 4 used in cooperation with the probe-type electrochemical sensor.
When in work, the probe type electrochemical sensor is particularly inserted in the micro reaction tank 4. The micro reaction tank 4 is filled with detection electrolyte to form an electrolytic tank, and the probe type electrochemical sensor extends into the electrolytic tank and can detect the catalytic reaction current of the electrolyte.
Specifically, the probe type electrochemical sensor comprises a pencil lead working electrode 1, an auxiliary electrode 2 and a reference electrode 3. The pencil lead working electrode 1 comprises a pencil lead 101 and an insulating tube 102, wherein the pencil lead 101 is a graphite pencil lead, and the diameter of the pencil lead is 0.3-1.0mm; the insulating tube 102 may be selected from, but not limited to, a plastic tube or a glass tube, and the insulating tube 102 is preferably a capillary tube, such as a plastic capillary tube or a glass capillary tube.
The pencil lead 101 is enclosed in the insulating tube 102, and both ends of the pencil lead 101 are exposed out of the insulating tube 102, and the length of the two points of the pencil lead 101 exposed out of the insulating tube 102 is preferably 2-5mm. And the gap between the pencil lead 101 and the insulating tube 102 is filled with epoxy resin and cured, so that the pencil lead 101 and the insulating tube 102 are kept in a relatively fixed arrangement.
And the auxiliary electrode 2 and the reference electrode 3 are formed on the outer wall of the insulating tube 102. Specifically, the auxiliary electrode 2 and the reference electrode 3 are formed by coating conductive silver paste on the outer wall of the insulating tube 102 and drying, and the auxiliary electrode 2 and the reference electrode 3 are independent and not connected to each other. Therefore, the auxiliary electrode 2, the reference electrode 3 and the pencil lead working electrode 1 are constructed on the insulating tube 102 in a highly integrated manner, and the use and the operation are convenient.
When the pencil lead detection device is used, the ends of the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3, which are inserted into the micro reaction tank 4, are detection ends. Preferably, when the pencil lead detection device works, the detection ends of the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3 are positioned at the position 5-15mm below the reaction liquid level. And the ends of the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3, which are positioned outside the micro reaction tank 4, are interface ends and are connected with an electrochemical workstation during working. In a preferred embodiment, the connecting ends of the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3, which are located outside the micro reaction cell 4, are respectively connected with a conductive patch 6 for electrically connecting with the electrochemical workstation, the conductive patch 6 is specifically a conductive metal sheet, such as a copper sheet, and the conductive patches 6 are respectively and correspondingly attached to the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3, so as to form interfaces respectively corresponding to the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3 and connected with the electrochemical workstation.
The micro reaction chamber 4 is specifically an insulating container such as a plastic tube, wherein the micro reaction chamber 4 has an open top, the probe-type electrochemical sensor is inserted from the top of the micro reaction chamber 4, and the sample solution for the detection work is also added from the top of the micro reaction chamber 4. The shape of the micro-reaction tank 4 can be any shape, for example, a circular plastic tube with a diameter of 1.0-1.5cm and a height of 1.0-2.0cm is adopted.
In a preferred embodiment, the micro-reaction wells 4 are provided with well covers 5, and the well covers 5 specifically snap-fit over the open top of the micro-reaction wells 4 and remain relatively fixed to the micro-reaction wells 4. Wherein, the cell cover 5 is provided with an electrode jack 501 and a sample adding hole 502, the electrode jack 501 is provided to have a hole diameter suitable for receiving the insertion of the probe-type electrochemical sensor, the sample adding hole 502 is provided to have a hole diameter capable of allowing the sample solution to pass through, and the hole diameters of the electrode jack 501 and the sample adding hole 502 are preferably 3-5mm. The probe-type electrochemical sensor is specifically inserted into the micro-reaction cell 4 from the electrode jack 501, and is assembled into an integral probe-type electrochemical detection device.
During working application, a sample solution to be detected is added into the micro reaction tank 4 from the sample adding hole 502, the generated catalytic current enables the pencil lead working electrode 1 to have a potential difference relative to the reference electrode 3, and the auxiliary electrode 2 is polarized, so that the voltage position of the catalytic current can be detected, and the concentration of the solution to be detected can be calculated.
Example two
The probe-type electrochemical detection device of the first embodiment is prepared by the following specific steps:
s1, inserting a graphite pencil lead into a plastic capillary, wherein two ends of the plastic capillary are exposed, and the exposed length is 2mm; wherein the diameter of the pencil lead is 0.5mm; filling epoxy resin into the capillary and curing to obtain a pencil lead working electrode;
s2, designing an auxiliary electrode and a reference electrode distribution area on the outer wall of the plastic capillary, wherein the auxiliary electrode, the reference electrode and the pencil lead working electrode are not connected with each other;
s3, uniformly coating conductive silver paste on the auxiliary electrode and the reference electrode area, and drying for 4 hours at 90 ℃ until the silver paste is completely dried, so as to obtain an auxiliary electrode and a reference electrode;
s4, connecting one sections of the pencil lead working electrode, the auxiliary electrode and the reference electrode by using a metal conductive patch to form an electrochemical workstation interface, wherein the other end is a working electrode reaction area, and thus, the probe type three-electrode electrochemical sensor is manufactured;
s5, punching the top of the plastic pipe with the cover to respectively obtain an electrode jack and a sample inlet hole, wherein the aperture is 3mm; the probe type three-electrode electrochemical sensor can be inserted into the electrode jack in a matching way, and then the probe type electrochemical detection device can be manufactured.
In a preferred embodiment, the probe-type three-electrode electrochemical sensor and the electrode jacks are filled with epoxy resin and fixed.
The schematic structure of the prepared probe-type electrochemical detection device is shown in fig. 1. The performance of the prepared probe-type electrochemical test device was measured using a potassium ferricyanide/potassium ferrocyanide electrochemical reaction indicator, and the cyclic voltammogram in a potassium ferricyanide/potassium ferrocyanide solution (concentration: 5 mM) is shown in fig. 2. As can be seen from fig. 2, the ratio of the absolute values of the measured redox peak currents is 0.95, which indicates that the potassium ferricyanide/potassium ferrocyanide undergoes a quasi-reversible reaction in the electrochemical reaction system, and the electrode potential is 0.11V (relative to the Ag reference electrode) and is close to the theoretical value, and this result indicates that the probe-type electrochemical detection device has good reliability.
EXAMPLE III
The hesperidin concentration is detected by adopting the probe type electrochemical detection device of the first embodiment, and the method comprises the following steps of:
s1, connecting a probe type electrochemical sensor with a corresponding interface of an electrochemical workstation through a conductive patch;
s2, adding 1500 mu L of phosphoric acid buffer solution with the concentration of 0.2M and the pH value of 6.9 into the micro reaction cell from the sample adding hole, and measuring a linear voltammetry curve of the blank solution under the conditions that the potential range is 0.6-0.1V and the scanning rate is 0.01V/S;
s3, adding different amounts of hesperidin solutions into the phosphate buffer solution from the sample adding hole respectively to obtain final concentrations of 0.0005mM, 0.001mM, 0.002mM, 0.005mM, 0.010mM, 0.020mM, 0.030mM, 0.040mM, 0.060mM, 0.080mM and 0.100mM, carrying out linear voltammetric scanning under the conditions that the potential range is 0.6-0.1V and the scanning rate is 0.01V/S, and measuring a current-voltage curve, wherein the current-voltage curve is shown in figure 3; wherein, as can be seen from the current-voltage curve of fig. 3, the obtained catalytic current increases with the increase of the concentration of the added hesperidin;
s4, cutting a catalytic curve, reading the peak current value of the linear voltammetry curve at different concentrations, and establishing a corresponding relation between the peak current value and the hesperidin concentration to obtain a concentration-current curve, wherein the concentration-current curve is shown in FIG. 4;
s5, performing linear fitting on the concentration-current curve, wherein in the detection range, the linear relation is as follows: y =0.0021x +2 × 10 -8 (R 2 = 0.96). Therefore, the electrochemical detection device can realize the linear detection of the hesperidin concentration within the range of 0.00005mM-0.100mM, and the detection sensitivity is 0.0021A/M;
s6, adding hesperidin solutions with the same concentration into three different electrochemical detection devices respectively to enable the target concentrations of the hesperidin solutions to be 0.075mM, and measuring the peak current values of the target hesperidin solutions to be 1.81 multiplied by 10 respectively -7 A、1.89×10 -7 A and 1.92X 10 -7 A (see FIG. 5), the obtained hesperidin concentrations were calculated at 0.076mM, 0.080mM and 0.082mM in comparison to the fitted curve, and the detection concentration of the target hesperidin solution was determined by taking the average value of 0.079 mM.
Furthermore, the recovery rate and the relative standard deviation of the obtained hesperidin concentration of 0.076mM, 0.080mM and 0.082mM are calculated, the recovery rate is 102%, 107% and 109%, and the relative standard deviation is +/-3%, so that the method has high corresponding accuracy and repeatability.
All the technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all the possible combinations of the technical features in the above embodiments are not described in this specification. However, as long as there is no contradiction between combinations of these technical features, the scope of the present specification should be considered as being described. Furthermore, the above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention.
It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A probe type electrochemical detection device is characterized by comprising a probe type electrochemical sensor and a matched micro reaction tank;
the probe type electrochemical sensor comprises a pencil lead working electrode, an auxiliary electrode and a reference electrode; the pencil lead working electrode comprises a pencil lead which is packaged in an insulating tube, two ends of the pencil lead are exposed out of the insulating tube, and the auxiliary electrode and the reference electrode are formed outside the insulating tube;
one end of the probe type electrochemical sensor is an interface end, and the other end of the probe type electrochemical sensor is a detection end; the pencil lead working electrode, the auxiliary electrode and the reference electrode are respectively connected with a conductive patch used for being electrically connected with an electrochemical workstation corresponding to the interface end of the probe type electrochemical sensor; when the probe type electrochemical sensor is used, the detection end of the probe type electrochemical sensor is inserted into the micro reaction tank.
2. The probe-type electrochemical detection device according to claim 1, wherein the space between the pencil lead and the insulation tube is filled with epoxy resin and cured.
3. The probe-type electrochemical detection device according to claim 1, wherein the auxiliary electrode and the reference electrode are conductive silver paste coated on the outer wall of the insulation tube and dried.
4. The probe-type electrochemical test device according to claim 1, wherein the insulating tube comprises a plastic tube or a glass tube.
5. The probe-type electrochemical detection device according to any one of claims 1-4, wherein the micro-reaction cell is configured with a cell cover, and the cell cover is provided with an electrode receptacle and a sample application hole; when in use, the detection end of the probe-type electrochemical sensor is inserted into the micro reaction cell from the electrode jack.
6. The preparation method of the probe type electrochemical detection device is characterized by comprising the following steps of:
s1, inserting a pencil lead into an insulating tube, wherein the pencil lead is exposed at two ends of the insulating tube, and filling and solidifying a gap between the pencil lead and the insulating tube to obtain a pencil lead working electrode;
s2, coating the auxiliary electrode conductive slurry and the reference electrode conductive slurry on two sides of the outer wall of the insulating tube, and drying to obtain an auxiliary electrode and a reference electrode;
s3, connecting conductive patches to one ends of the pencil lead working electrode, the auxiliary electrode and the reference electrode to obtain the probe type electrochemical sensor;
and S4, adopting an insulating container as a micro reaction tank, and enabling one end of the probe-type electrochemical sensor, which is not provided with the conductive patch, to be inserted into the micro reaction tank in a matched manner, so as to obtain the probe-type electrochemical detection device.
7. The method for preparing the probe-type electrochemical detection device according to claim 6, wherein the auxiliary electrode conductive paste and the reference electrode conductive paste are conductive silver pastes, and the drying is performed at 80-120 ℃ for 1-5 hours.
8. The method for preparing a probe-type electrochemical detection device according to claim 6 or 7, wherein a cell cover is disposed on the micro-reaction cell, and the cell cover has an electrode receptacle and a sample application hole; when the probe type electrochemical sensor is used, one end of the probe type electrochemical sensor, which is not provided with the conductive patch, is inserted into the micro reaction cell from the electrode jack.
9. The application of the probe-type electrochemical detection device of any one of claims 1 to 5 in rapid detection of hesperidin concentration, which is characterized by comprising the following steps:
s1, inserting a detection end of the probe-type electrochemical sensor into the micro reaction tank, assembling the probe-type electrochemical detection device, and connecting the probe-type electrochemical sensor with an electrochemical workstation;
s2, adding a buffer solution into the micro reaction tank, and measuring and obtaining a voltammetry curve of a blank solution;
s3, adding hesperidin solutions with different concentrations into the micro reaction tank, and measuring and obtaining voltammetry curves of the hesperidin solutions with different concentrations;
s4, determining catalytic current values corresponding to the voltammetry curves according to the corresponding voltammetry curves of the hesperidin solutions with different concentrations, further determining the relation between the hesperidin concentration and the catalytic current, and making a concentration-current curve;
s5, performing linear fitting on the obtained concentration-current curve to obtain a fitting curve;
s6, respectively adding target hesperidin solutions with the same concentration into at least three probe-type electrochemical detection devices, contrasting the fitted curve according to the peak current value of the measured target hesperidin solution to obtain corresponding hesperidin concentrations, and calculating an average value, wherein the average value is determined as the detection concentration of the target hesperidin solution.
10. The use of claim 9, wherein the buffer solution comprises a phosphate buffer solution having a pH of 6.9; and/or the voltammetry curve comprises cyclic voltammetry curve or linear voltammetry scanning curve, and the voltammetry curve is obtained by measuring under the conditions that the potential range is 0.6-0.1V and the scanning rate is 0.01V/s.
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