CN115791916B - 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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- QUQPHWDTPGMPEX-UHFFFAOYSA-N Hesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(COC4C(C(O)C(O)C(C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-UHFFFAOYSA-N 0.000 claims abstract description 49
- QUQPHWDTPGMPEX-UTWYECKDSA-N aurantiamarin Natural products COc1ccc(cc1O)[C@H]1CC(=O)c2c(O)cc(O[C@@H]3O[C@H](CO[C@@H]4O[C@@H](C)[C@H](O)[C@@H](O)[C@H]4O)[C@@H](O)[C@H](O)[C@H]3O)cc2O1 QUQPHWDTPGMPEX-UTWYECKDSA-N 0.000 claims abstract description 49
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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 miniature 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 flow, quick response, high sensitivity and the like when in detection use, and can realize quick and accurate detection. The preparation method can realize the efficient assembly of the probe type electrochemical detection device, and the performance of the prepared 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 sensitivity response, wide linear range, high recovery rate, low relative deviation and the like to the hesperidin in the solution, and can realize the rapid detection of 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 continuous enhancement of health consciousness of people, the requirements of people on food quality are higher and higher. Natural antioxidants are a class of physiologically active substances, including flavonoids, that are widely found in agricultural by-products such as vegetables, fruits, and tea. Research shows that the natural antioxidant has important functions in preventing cancer, cardiac and cerebral vascular diseases, delaying senility, promoting metabolism, etc. Thus, the content of natural antioxidants often determines the quality of these agricultural by-products and their processed products.
The traditional analysis and detection methods for the content of the natural antioxidant comprise ultraviolet-visible spectrophotometry, high performance liquid chromatography, gas chromatography and the like, and the methods generally have the problems of complicated sample treatment, complex instrument and equipment, long analysis and detection time, high cost and the like, and are especially not suitable for the rapid measurement of the content of the antioxidant in food and agricultural products in daily life.
In recent years, electrochemical-based analysis techniques have been attracting attention, but at present, there is no conventional electrochemical device suitable for rapid detection of natural antioxidants including flavonoids, and the detection accuracy is low, and at the same time, the preparation method of the conventional electrochemical detection device is complicated and generally expensive, which limits its wide use in practical production.
Disclosure of Invention
The invention aims to solve the problems of low detection efficiency, low electrochemical detection precision, high cost and the like of the prior art on natural antioxidants such as flavonoids and the like.
Another object of the present invention is to provide a method for manufacturing the above-mentioned probe-type electrochemical detection device, which can be used for mass production of the probe-type electrochemical detection device.
The invention also aims to provide the application of the probe type electrochemical detection device, which can be particularly applied to the rapid detection of the concentration of hesperidin in a solution.
The aim of the invention is achieved by the following technical scheme.
A probe type electrochemical detection device comprises a probe type electrochemical sensor and a miniature 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 and 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 used for being electrically connected with an electrochemical workstation; when in use, the detection end of the probe type electrochemical sensor is inserted into the miniature reaction tank.
In a preferred embodiment, the space between the pencil lead and the insulating tube is filled with epoxy 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 according to any one of the above embodiments, wherein a cell cover is disposed on the micro-reaction cell, and the cell cover has an electrode insertion hole and a sample addition hole; when the probe type electrochemical sensor is used, the detection end of the probe type electrochemical sensor extends into the miniature reaction tank from the electrode jack.
A preparation method of a probe type electrochemical detection device comprises the following steps:
s1, penetrating 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 conductive paste of the auxiliary electrode and the conductive paste of the reference electrode on two sides of the outer wall of the insulating tube, and drying to obtain the auxiliary electrode and the reference electrode, wherein the auxiliary electrode and the reference electrode are not connected with each other;
s3, connecting conductive patches on one ends of the pencil lead working electrode, the auxiliary electrode and the reference electrode to obtain a probe-type electrochemical sensor;
s4, adopting an insulating container as a miniature reaction tank, and enabling one end of the probe type electrochemical sensor, which is not connected with the conductive patch, to be inserted into the miniature 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 paste, 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, the method for manufacturing a probe-type electrochemical detection device according to any one of the above embodiments, wherein a cell cover is disposed on the micro-reaction cell, and the cell cover has an electrode insertion hole and a sample application hole; when the probe type electrochemical sensor is used, one end of the probe type electrochemical sensor, which is not connected with the conductive patch, is inserted into the miniature reaction tank from the electrode jack.
The use of the probe-type electrochemical detection device according to any of the above, including use in food detection and agricultural product detection.
The application of the probe-type electrochemical detection device in the rapid detection of the hesperidin concentration is specifically that the hesperidin is subjected to electrocatalytic oxidation reaction at a pencil lead working electrode of the probe-type electrochemical detection device to generate catalytic current, the detected substance can be judged to be hesperidin according to the voltage position when the catalytic current is generated, and the concentration of the hesperidin can be calculated and obtained according to the generated catalytic current. The application of the method in rapid detection of the concentration of hesperidin comprises the following steps:
s1, inserting a detection end of the probe type electrochemical sensor into the miniature 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 miniature reaction tank of the probe type electrochemical detection device, and measuring and obtaining a voltammogram of a blank solution;
s3, adding hesperidin solutions with different concentrations into a miniature reaction tank of the probe type electrochemical detection device, and measuring and obtaining volt-ampere curves of the hesperidin solutions with different concentrations;
s4, determining corresponding catalytic current values of all volt-ampere curves according to the volt-ampere curves corresponding to the hesperidin solutions with different concentrations, further determining the relation between the hesperidin concentration and the catalytic current, and manufacturing a concentration-current curve;
s5, performing linear fitting on the obtained concentration-current curve to obtain a fitted curve;
s6, respectively adding target hesperidin solutions with the same concentration into at least three probe-type electrochemical detection devices, obtaining corresponding hesperidin concentrations according to the measured peak current values of the target hesperidin solutions by comparing with the fitting curve, and calculating an average value, wherein the average value is determined to be the detection concentration of the target hesperidin solutions.
In a preferred embodiment, the buffer solution comprises a phosphate buffer solution having a pH of 6.9.
In a particularly preferred embodiment, the phosphate buffer solution having a pH of 6.9 has a concentration of 0.2M (M=mol/dm 3 ) The addition amount was 1000. Mu.L to 1500. Mu.L (L=dm) 3 )。
In a preferred embodiment, the voltammogram comprises a cyclic voltammogram or a linear voltammogram, the voltammogram being obtained by measurement at a potential in the range of 0.6-0.1V and a sweep rate of 0.01V/s.
In a preferred embodiment, in S6, after obtaining the hesperidin concentrations corresponding to at least three of the probe-type electrochemical detection devices, respectively, recovery rates and relative standard deviations are calculated, and the accuracy and repeatability of the probe-type electrochemical detection devices 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, has simple detection operation flow, quick response and high sensitivity, can realize quick and accurate detection, can be used in the quality control fields including food detection, agricultural product detection and the like, is particularly suitable for quick evaluation of food and drug 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 probe type electrochemical detection device can be measured by adopting common electrochemical indicators such as potassium ferricyanide, so that the probe type electrochemical detection device can be produced in a large scale and high efficiency, and the wide application of the probe type electrochemical detection device is facilitated.
The probe type of the inventionThe electrochemical detection device has high sensitivity response (the sensitivity reaches 0.0021A/M) to hesperidin in solution, and has 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) and low relative deviation (the relative standard deviation is within +/-3%, namely the repeatability is high), and the like, and the rapid detection of hesperidin in the solution can be realized.
Drawings
FIG. 1 is a schematic diagram of a probe-type electrochemical detection device according to the present invention in a first embodiment;
FIG. 2 is a cyclic voltammogram of potassium ferricyanide/potassium ferrocyanide prepared in example two;
FIG. 3 is a graph showing the linear voltammogram of the test hesperidin solution in example III;
FIG. 4 is a graph showing the concentration-current relationship of hesperidin solution detected in example III;
FIG. 5 is a graph showing the detection of hesperidin solution in the third embodiment.
The drawings are marked: 1-pencil lead working electrode, 101-pencil lead, 102-insulating tube, 2-auxiliary electrode, 3-reference electrode, 4-miniature reaction tank, 5-tank cover, 501-electrode jack, 502-sample adding hole and 6-conductive patch.
Detailed Description
The technical scheme of the present invention will be described in further detail with reference to specific examples, but the scope and embodiments of the present invention are not limited thereto. This 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 will be apparent to those of ordinary skill in the art that the drawings in the following description are only a few embodiments of the present invention and that other drawings may be derived from these drawings without the exercise of inventive faculty.
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 reagents, equipment and methods used in this invention are those conventionally commercially available in the art. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Unless otherwise specified, all technical and scientific terms used herein have the standard meaning of the art to which the claimed subject matter belongs. In case there are multiple definitions for a term, the definitions herein control.
The present invention employs, unless otherwise indicated, standard nomenclature for analytical chemistry, organic synthetic chemistry and optics, and standard laboratory procedures and techniques.
As used herein, the singular forms "a", "an", and "the" are understood to include plural referents unless the context clearly dictates otherwise. Furthermore, the terms "comprising," "including," "having," and "containing" are intended to be open-ended, i.e., to include the meaning of the terms noted herein, but not to exclude other elements. In other words, the term also includes "consisting essentially of …," or "consisting of …. In addition, "and combinations thereof" in the specification refer to any combination of all the items listed.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
Example 1
Referring to fig. 1, the probe-type electrochemical detection device of the present invention includes a probe-type electrochemical sensor and a micro reaction tank 4 for use with the probe-type electrochemical sensor.
In operation, the probe-type electrochemical sensor is specifically inserted into the miniature reaction cell 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 includes 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 specifically a graphite pencil lead with the diameter of 0.3-1.0mm; the insulating tube 102 is optionally, but not limited to, a plastic or glass tube, and the insulating tube 102 is preferably a capillary tube, such as a plastic or glass capillary tube.
The pencil core 101 is enclosed in the insulating tube 102 with both ends exposed to the outside of the insulating tube 102, and the length of the two points of the pencil core 101 exposed from the insulating tube 102 is preferably 2-5mm. And the gap between the pencil core 101 and the insulating tube 102 is filled with epoxy resin and cured, so that the pencil core 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 mutually independent and are not mutually connected. Thus, 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 operation are convenient.
When in use, one end of the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3, which is inserted into the miniature reaction tank 4, is a detection end. Preferably, in operation, the detection ends of the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3 are located 5-15mm below the reaction liquid level. And one end of the pencil core working electrode 1, the auxiliary electrode 2 and the reference electrode 3, which is positioned outside the miniature reaction tank 4, is an interface end and is connected with an electrochemical workstation in working. In a preferred embodiment, the connection ends of the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3, which are positioned outside the miniature reaction tank 4, are respectively connected with a conductive patch 6 for being electrically connected with an electrochemical working station, the conductive patch 6 is specifically a conductive metal sheet, such as a copper sheet, and the like, and the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3 are respectively and correspondingly attached with the conductive patch 6, so that interfaces of the pencil lead working electrode 1, the auxiliary electrode 2 and the reference electrode 3, which are respectively and correspondingly connected with the electrochemical working station, are formed.
The micro-reaction cell 4 is specifically an insulating container such as a plastic tube, wherein the micro-reaction cell 4 has an open top, a probe-type electrochemical sensor is inserted from the top of the micro-reaction cell 4, and a sample solution in a detection operation is also added from the top of the micro-reaction cell 4. And the shape of the micro reaction tank 4 can be any shape, such as a circular plastic pipe with the diameter of 1.0-1.5cm and the height of 1.0-2.0 cm.
In a preferred embodiment, the micro-reaction chamber 4 is provided with a chamber cover 5, and the chamber cover 5 specifically covers the open top of the micro-reaction chamber 4 in a snap-fit manner and keeps relatively fixed with respect to the micro-reaction chamber 4. Wherein, an electrode jack 501 and a sample adding hole 502 are arranged on the cell cover 5, the electrode jack 501 is arranged to enable the aperture of the electrode jack to be adaptive to accommodate the insertion of the probe type electrochemical sensor, the sample adding hole 502 is arranged to enable the aperture of the sample adding hole 502 to specifically allow the fed sample liquid to pass through, and the aperture of the electrode jack 501 and the aperture of 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 insertion hole 501, and is assembled into an integrated probe-type electrochemical detection device.
When the pencil lead detection device is in working application, the sample liquid to be detected is added into the miniature reaction tank 4 from the sample adding hole 502, the generated catalytic current enables the pencil lead working electrode 1 to have 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 and obtained.
Example two
The probe-type electrochemical detection device according to the first embodiment is prepared by the following steps:
s1, inserting a graphite pencil core into a plastic capillary, and exposing the two ends of the plastic capillary, wherein the exposed length is 2mm; wherein, the diameter of the pencil core is 0.5mm; filling the interior of the capillary tube with epoxy resin 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 core working electrode are not connected with each other;
s3, uniformly coating conductive silver paste on the auxiliary electrode and reference electrode areas, and drying at 90 ℃ for 4 hours until the silver paste is completely dried to obtain an auxiliary electrode and a reference electrode;
s4, connecting one section 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, so as to prepare the probe type three-electrode electrochemical sensor;
s5, punching the top of the plastic pipe with the cover to respectively obtain an electrode jack and a sample injection hole, wherein the aperture is 3mm; the probe type three-electrode electrochemical sensor can be inserted into the electrode jack in an adaptive manner, and the probe type electrochemical detection device can be manufactured.
In a preferred embodiment, the space between the probe-type three-electrode electrochemical sensor and the electrode insertion hole is filled and fixed with epoxy resin.
The schematic structure of the prepared probe type electrochemical detection device is shown in fig. 1. The performance of the prepared probe-type electrochemical detection device was measured using a potassium ferricyanide/potassium ferrocyanide electrochemical reaction indicator, and its 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 value of the redox peak current is 0.95, which indicates that the potassium ferricyanide/potassium ferrocyanide has a quasi-reversible reaction in the electrochemical reaction system, and the electrode potential is 0.11V (relative to the Ag reference electrode) which is close to the theoretical value, and the result indicates that the probe-type electrochemical detection device has good reliability.
Example III
The probe-type electrochemical detection device of the first embodiment is used for detecting the concentration of hesperidin, and the steps are as follows:
s1, connecting a probe type electrochemical sensor with an interface corresponding to an electrochemical workstation through a conductive patch;
s2, adding 1500 mu L of phosphoric acid buffer solution with the concentration of 0.2 and M, pH value of 6.9 into the micro reaction tank from the sample adding hole, and measuring the linear voltammogram of the blank solution under the conditions of the potential range of 0.6-0.1V and the scanning rate of 0.01V/S;
s3, respectively adding different amounts of hesperidin solution from the sample adding hole to the phosphoric acid buffer solution, and carrying out linear voltammetry scanning under the conditions of potential range of 0.6-0.1V and scanning speed of 0.01V/S to obtain current-voltage curve, wherein the final concentration is 0.0005mM, 0.001mM, 0.002mM, 0.005mM, 0.010mM, 0.020mM, 0.030mM, 0.040mM, 0.060mM, 0.080mM and 0.100mM, and the current-voltage curve is measured as shown in figure 3; it can be seen from the current-voltage curve of fig. 3 that the catalytic current obtained increases with increasing concentration of added hesperidin;
s4, reading peak current values of the linear volt-ampere curves under different concentrations by making tangents to the catalytic curves, and establishing a corresponding relation between the peak current values and the hesperidin concentration to obtain a concentration-current curve, as shown in FIG. 4;
s5, performing linear fitting on a concentration-current curve, wherein in a 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 linear detection of the concentration of the hesperidin within the range of 0.00005mM-0.100mM, and the detection sensitivity is 0.0021A/M;
s6, respectively adding the hesperidin solutions with the same concentration into three different electrochemical detection devices to ensure that the target concentrations are 0.075mM, and respectively measuring the peak current values of the target hesperidin solutions to be 1.81 multiplied by 10 -7 A、1.89×10 -7 A and 1.92×10 -7 A (see FIG. 5), and comparing the calculated hesperidin concentrations with the fitted curve of 0.076mM, 0.080mM and 0.082mM, and taking the average value of 0.079mM to determine the detection concentration of the target hesperidin solution.
Further, the recovery rates and the relative standard deviation of the obtained hesperidin concentrations of 0.076mM, 0.080mM and 0.082mM were calculated, and the recovery rates were 102%, 107% and 109%, respectively, and the relative standard deviation was.+ -. 3%, respectively, with high corresponding accuracy and reproducibility.
The technical features of the foregoing embodiments may be combined in any manner, and in this specification, for brevity, all of the possible combinations of the technical features of the foregoing embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, it should be considered as the scope described in the present specification. Moreover, the foregoing examples represent only a few embodiments of the present invention, which are described in detail and are not thereby to be construed as limiting the scope of the invention.
It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. The application of the probe type electrochemical detection device in the rapid detection of the hesperidin concentration is characterized in that the probe type electrochemical detection device comprises a probe type electrochemical sensor and a matched miniature 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 and 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; the auxiliary electrode and the reference electrode are conductive silver paste coated on the outer wall of the insulating tube and dried;
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 used for being electrically connected with an electrochemical workstation; when in use, the detection end of the probe type electrochemical sensor is inserted into the miniature reaction tank;
the application of the probe type electrochemical detection device in the rapid detection of the hesperidin concentration comprises the following steps:
s1, inserting a detection end of the probe type electrochemical sensor into the miniature 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 miniature reaction tank, and measuring and obtaining a voltammogram of a blank solution;
s3, adding hesperidin solutions with different concentrations into the miniature reaction tank, and measuring and obtaining volt-ampere curves of the hesperidin solutions with different concentrations;
s4, determining corresponding catalytic current values of all volt-ampere curves according to the volt-ampere curves corresponding to the hesperidin solutions with different concentrations, further determining the relation between the hesperidin concentration and the catalytic current, and manufacturing a concentration-current curve;
s5, performing linear fitting on the obtained concentration-current curve to obtain a fitted curve;
s6, respectively adding target hesperidin solutions with the same concentration into at least three probe-type electrochemical detection devices, obtaining corresponding hesperidin concentrations according to the measured peak current values of the target hesperidin solutions by comparing with the fitting curve, and calculating an average value, wherein the average value is determined to be the detection concentration of the target hesperidin solutions.
2. The use of the probe-type electrochemical detection apparatus according to claim 1 for rapid detection of hesperidin concentration, characterized in that the space between the pencil lead and the insulating tube is filled with epoxy resin and cured.
3. The use of the probe-type electrochemical detection apparatus according to claim 1 for rapid detection of hesperidin concentration, wherein the insulating tube comprises a plastic tube or a glass tube.
4. The use of the probe-type electrochemical detection device according to any one of claims 1 to 3 for rapid detection of hesperidin concentration, wherein a cell cover is disposed on the miniature reaction cell, and the cell cover is provided with an electrode jack and a sample application hole; when the probe type electrochemical sensor is used, the detection end of the probe type electrochemical sensor is inserted into the miniature reaction tank from the electrode jack.
5. The use of a probe-type electrochemical detection device according to claim 1 for rapid detection of hesperidin concentration, wherein the preparation method of the probe-type electrochemical detection device comprises the following steps:
s1, penetrating 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 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;
s3, connecting conductive patches on one ends of the pencil lead working electrode, the auxiliary electrode and the reference electrode to obtain a probe-type electrochemical sensor;
s4, adopting an insulating container as a miniature reaction tank, and enabling one end of the probe type electrochemical sensor, which is not connected with the conductive patch, to be inserted into the miniature reaction tank in a matched manner, so as to obtain the probe type electrochemical detection device.
6. The use of a probe-type electrochemical detection apparatus for rapid detection of hesperidin concentration according to claim 5, wherein the auxiliary electrode conductive paste and the reference electrode conductive paste are conductive silver paste, and the drying is performed at 80-120 ℃ for 1-5 hours.
7. The use of a probe-type electrochemical detection apparatus according to claim 5 or 6 for rapid detection of hesperidin concentration, wherein a cell cover is disposed on the miniature reaction cell, and the cell cover has an electrode insertion hole and a sample application hole; when the probe type electrochemical sensor is used, one end of the probe type electrochemical sensor, which is not connected with the conductive patch, is inserted into the miniature reaction tank from the electrode jack.
8. The use of a probe-type electrochemical detection apparatus according to claim 1 for rapid detection of hesperidin concentration, wherein the buffer solution comprises a phosphate buffer solution having a pH of 6.9; and/or the voltammogram comprises a cyclic voltammogram or a linear voltammogram, the voltammogram being obtained by measurement at a potential in the range of 0.6-0.1V and a sweep rate of 0.01V/s.
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