CN109541006B - Novel electrode for measuring metformin hydrochloride and measuring method thereof - Google Patents
Novel electrode for measuring metformin hydrochloride and measuring method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a novel electrode for measuring metformin hydrochloride and an electrochemical method thereof. The measuring system consists of an N-N dimethylformamide/nano-silver modified conductive glass electrode as a working electrode, a saturated calomel electrode as a reference electrode and a platinum wire electrode as a counter electrode. The method comprises the steps of taking PBS with pH of 6.64 as a buffer solution, and measuring the oxidation peak current of a cyclic voltammetry curve under the conditions that the potential is within the range of 0-1V and the scanning speed is 50 mV/s. The concentration of the metformin hydrochloride is in a range of 0.075-0.2 mg/mL, and the linear relation is good. Its standard curve equation is y =31.719x +3.0076, R = 0.9595. The average recovery rate of metformin hydrochloride content in the same batch of samples measured 10 times is 103.5%, and the relative standard deviation RSD value is 4.2%. The electrode can be applied to the determination of the content of the active ingredients in the metformin hydrochloride drug sample.
Description
Technical Field
The invention relates to the technical field of electrochemical analysis and detection, in particular to a novel electrode for measuring metformin hydrochloride, and a preparation method and a detection method of the electrode.
Background
Metformin hydrochloride is a commonly used medicine for reducing blood sugar, is mainly used for type II diabetes patients with hyperglycemia after fasting and meals, has certain curative effect particularly for patients with obesity and hyperinsulinemia, and not only can be used for reducing blood sugar, but also can reduce obesity and relieve hyperinsulinemia. At present, people have made a great deal of research on the detection of metformin hydrochloride, and a plurality of detection methods of metformin hydrochloride are developed, mainly including a reversed phase-high performance liquid chromatography, an HPLC method, a capillary electrophoresis method, an ultraviolet spectrophotometry method and an electrochemical method. Compared with other methods, the stability and sensitivity of the electrochemical method for detecting the metformin hydrochloride are greatly improved, so that great attention is paid to the field of metformin hydrochloride detection, and great development is achieved.
Disclosure of Invention
The invention aims to provide an electrochemical analysis method which has high selectivity and high sensitivity on metformin hydrochloride and is relatively easy to operate.
In order to achieve the purpose, the invention adopts the technical scheme that: the novel electrode for measuring the metformin hydrochloride comprises a three-electrode system consisting of an N-N dimethylformamide/nano-silver modified conductive glass electrode as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode.
Further, the preparation method of the N-N dimethylformamide/nano silver electrode comprises the following steps: a three-electrode system consisting of a platinum wire electrode serving as a counter electrode and a saturated calomel electrode serving as a reference electrode is placed in N-N dimethylformamide; circularly scanning for 5 weeks at a sweeping speed of 100mV/s between 0-1V potential ranges until the cyclic voltammetry curve is stable; taking out the electrode, placing the electrode in a silver nitrate solution of 5mmol/L under a static condition, and in a potential range of-0.2 to-0.8V, wherein the linear dissolution sweep rate is 0.5mV/s, and the dissolution time is 180s, and finally obtaining the N-N dimethylformamide/nano silver electrode.
The method for measuring the metformin hydrochloride by using the novel electrode for measuring the metformin hydrochloride comprises the following steps: placing an N-N dimethylformamide/nano-silver modified conductive glass electrode system in a standard solution of metformin hydrochloride with the concentration of 0.075-0.2 mg/mL, taking PBS with the pH of 6.64 as a buffer solution, recording the oxidation peak current of a cyclic voltammetry curve under the conditions that the potential range is 0-1V and the scanning speed is 50mV/s, and then drawing a standard curve by taking the current value to the concentration of the standard product, wherein the standard curve is that y is 31.719x +3.0076, R is 31.719x +3.00762Under the same experimental conditions, the peak current of the sample was measured and the sample content was calculated using the standard curve equation.
The invention utilizes the good conductivity of the conductive glass electrode and combines the properties of N-N dimethylformamide and silver nitrate to prepare the electrode with high sensitivity to the metformin hydrochloride. Then, by optimizing the parameters of N-N dimethylformamide such as the number of scanning circles, the type of buffer solution, the scanning speed, the pH value of base solution and the like, the electrochemical analysis method which has higher selectivity and higher sensitivity to N-N dimethylformamide and is easier to operate is obtained, and the method is applied to the determination of actual samples.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a cyclic voltammogram of different electrodes in potassium ferricyanide solution.
The sequence of the oxidation peak current values in the cyclic voltammetry curve from high to low corresponds to 1-5 working electrodes respectively. The curve 1 is an N-N dimethylformamide/nano silver modified conductive glass electrode; curve 2 is a N-N dimethylformamide modified conductive glass electrode; curve 3 is a nano-silver modified conductive glass electrode; curve 4 is a nano-silver/N-N dimethylformamide modified conductive glass electrode; curve 5 is a bare conductive glass electrode.
FIG. 2 is a graph of cyclic voltammograms of different electrodes in a 0.1mg/mL solution of metformin hydrochloride.
(a) Modifying the conductive glass electrode by nano silver; (b) N-N dimethylformamide/nano silver modified conductive glass electrode; (c) modifying the conductive glass electrode by nano silver/N-N dimethylformamide; (d) N-N dimethylformamide modifies the conductive glass electrode; (e) a bare conductive glass electrode.
FIG. 3 is a scanning diagram of metformin hydrochloride with different concentrations on a modified nano-silver electrode.
FIG. 4 is an optimized pH curve.
FIG. 5 is a graph of the thickness optimization of the polymeric film (N-N dimethylformamide).
FIG. 6 is a CV diagram of metformin hydrochloride solutions of different concentrations.
FIG. 7 is a standard curve drawn by the oxidation peak of the voltammetric analysis graph of metformin hydrochloride solutions of different concentrations by using N-N dimethylformamide/nano silver modified conductive glass electrode.
Detailed Description
The implementation idea of the invention is as follows:
preparing a sensor: purifying a glass electrode (ITO), scanning N-N dimethylformamide by cyclic voltammetry, and preparing an N-N dimethylformamide/nano silver modified electrode by electrodeposition;
optimization of assay conditions: the kind of the buffer solution, the influence of pH, the influence of the number of turns of modified nitrogen and the influence of scanning speed;
determination of the actual sample: the working electrode is an N-N dimethylformamide/nano-silver modified electrode which takes conductive glass (ITO) as a substrate electrode, the reference electrode is a Saturated Calomel Electrode (SCE), and the counter electrode is a platinum wire electrode, so that a three-electrode system is assembled; the three-electrode system was placed in PBS (2X 10) at pH 6.64-6g/ml catechol) buffer solution, and recording a cyclic voltammetry curve of peak current in a range of 0.05-0.2 mg/ml under the optimal experimental conditions.
Specifically, the method comprises the following steps:
purification of the glass electrode: conducting glass (ITO) is sequentially cleaned by detergent, dilute hydrochloric acid, ethanol and deionized water for 5min in an ultrasonic mode, and dried by cold air.
Preparing an N-N dimethylformamide/nano-silver modified electrode: the whole preparation process is carried out by utilizing a CS300 electrochemical workstation, and a three-electrode system is adopted: the conductive glass (ITO) is used as a substrate electrode and is used as a working electrode, the platinum wire electrode is used as a counter electrode, and the Saturated Calomel Electrode (SCE) is used as a reference electrode. Firstly, the assembled three-electrode system is put into N-N dimethylformamide and is cyclically scanned for 5 weeks at a sweep rate of 100mV/s between the potential ranges of 0V and 1V under a static condition until a cyclic voltammetry curve is stable, the electrode is taken out, and then the electrode is put into a silver nitrate solution of 5mmol/L under the static condition, between the potential ranges of-0.2V to-0.8V, the linear dissolution sweep rate is 0.5mV/s, and the dissolution time is 180 s. So as to prepare the N-N dimethylformamide/nano silver electrode.
As shown in fig. 1, cyclic voltammograms of different electrodes in potassium ferricyanide solution. Sequentially using 1.N-N dimethylformamide/nano silver electrode; an N-N dimethylformamide electrode; 3. a nano-silver electrode; 4. a nano-silver/N-N dimethylformamide electrode; 5. bare glass electrode at 1.5X 10-2mol/L K3[Fe(CN)6]And (3) scanning the solution by cyclic voltammetry (the current potential is 0-1V, and the scanning speed is 50 mV/s). In the figure, N-N dimethylformamide electrode (curve 2), nano silver electrode (curve 3) nano silver/N-N dimethyl methylThe current of the redox peak of the amide electrode (curve 4) is increased compared with that of the bare glass electrode (curve 5), which shows that N-N dimethylformamide, nano silver and nano silver/N-N dimethylformamide are respectively polymerized on the surface of the glass electrode, and the redox of probe ions on the surface of the electrode is promoted. And when the oxidation current peak of the N-N dimethylformamide/nano silver electrode (curve 1) obtained by modifying silver nitrate on the surface of the N-N dimethylformamide is the highest, but the reduction peak of the N-N dimethylformamide/nano silver electrode (curve 1) is lower than that of other electrodes (higher than that of a bare glass electrode curve 5) from the figure, which indicates that the conductivity (oxidation current) is the best when the N-N dimethylformamide/nano silver electrode is modified by the nano silver.
As shown in FIG. 2, cyclic voltammograms of different electrodes in 0.1mg/mL metformin hydrochloride solution. Preparing a 0.1mg/mL metformin hydrochloride solution by using a pH 6.64 (catechol) buffer solution, sequentially scanning by using a modified nano-silver electrode, an N-N dimethylformamide/nano-silver electrode, an N-N dimethylformamide electrode and a bare conductive glass electrode, scanning by using a nano-silver/N-dimethylformamide electrode and a nano-silver/N-dimethylformamide electrode at a scanning speed of 50mV/s within a potential range of 0-1V, wherein the peak type of the N-N dimethylformamide/nano-silver electrode is the best, (d) the N-N dimethylformamide/nano-silver electrode and the bare conductive glass electrode do not generate a peak in a scanned sample, (c) the oxidation peak of the nano-silver/N-dimethylformamide electrode in the sample is lower than that of the N-N dimethylformamide/nano-silver electrode, (a) the oxidation peak of the nano silver electrode is higher than that of the nano silver electrode (b).
As shown in fig. 3, the scanning curves of metformin hydrochloride with different concentrations on the modified nano-silver electrode are shown. Linear plots (linear plots from oxidation peak current values) of cyclic voltammetric scans using nanosilver against 0.075mg/mL, 0.1mg/mL, 0.15mg/mL, 0.2mg/mL metformin hydrochloride solution formulated under the conditions described above. From the figure, it can be seen that the linear equation of the oxidation peak is y-129.98 x +86.016, R20.4108, it can be concluded that the linearity of the silver electrode is not good.
In conclusion, the best response of the N-N dimethylformamide/nano silver electrode to the metformin hydrochloride can be known from the attached drawings 1, 2 and 3.
As shown in FIG. 4, the conditions for pH optimization. And (3) carrying out cyclic voltammetry scanning on a 0.1mg/mL metformin hydrochloride solution prepared from a PBS (containing catechol) buffer solution with the pH range of 5-9 by using an N-N dimethylformamide/nano silver electrode to obtain a curve. It can be seen from the figure that the oxidation peak current increases with increasing pH of the buffer solution and decreases when the pH is greater than 6.64. From this result, it was found that N-N dimethylformamide/nano silver electrode responded best to metformin hydrochloride when the pH of the buffer solution was 6.64. Therefore, this invention uses a PBS (containing catechol) buffer solution with a pH of 6.64 as a base solution to measure metformin hydrochloride.
As shown in FIG. 5, the thickness of the polymeric film (N-N dimethylformamide) is optimized. And (3) obtaining curves obtained by respectively carrying out cyclic voltammetry scanning on the N-N dimethylformamide/nano silver electrode in a metformin hydrochloride solution of 0.1mg/mL (with different film thicknesses) by changing the number of cyclic voltammetry scanning circles in the N-N dimethylformamide only and changing the number of the circles to be 1-15 circles. It can be seen from the figure that the oxidation peak current is increasing with the number of scanning turns and decreasing when the number of turns is more than 5. From this, it was found that the N-N dimethylformamide/nanosilver electrode responded best to metformin hydrochloride when the number of scanning cycles was 5. The experiment was performed with 5 scans to prepare the electrodes.
As shown in FIG. 6, CV diagrams of metformin hydrochloride solutions of different concentrations. The time current diagram of the oxidation peak is taken. Solutions of metformin hydrochloride having a solution concentration of 0.05mg/mL (curve 5), 0.075mg/mL (curve 4), 0.1mg/mL (curve 3), 0.15mg/mL (curve 2), 0.2mg/mL (curve 1) were prepared from PBS (catechol) buffer solution having a pH of 6.64, and the metformin hydrochloride solutions having different concentrations were subjected to modified electrode measurement using cyclic voltammetry under optimum experimental conditions. It can be seen from the figure that as the concentration of the metformin hydrochloride solution increases, the peak current increases in sequence and the peak pattern is good, and the N-N dimethylformamide/nano silver electrode can be judged from the graph to have high sensitivity for measuring the metformin hydrochloride medicament.
FIG. 7 is a standard curve. Oxidation peak of voltammetric characteristic analysis chart of metformin hydrochloride solution with different concentrations by using N-N dimethylformamide/nano silver electrodeAnd drawing a standard curve chart by using drawing software. It can be seen from the figure that the peak current is also increased along with the increase of the concentration of the metformin hydrochloride, the concentration of the metformin hydrochloride and the magnitude of the peak current show a positive correlation trend, and the standard curve of the modified electrode scanning solutions with different concentrations of the metformin hydrochloride is 31.719x +3.0076, R20.9595(Y is current, with unit 10)-5A; x is metformin hydrochloride concentration in mg/mL).
From the attached figures 6 and 7, the N-N dimethylformamide/nano silver electrode can be judged to have good measurement precision and stability on the metformin hydrochloride.
Under the optimal experimental conditions obtained from the above experiments, the oxidation peak current 6.2112X 10 of a formulated labeled concentration of metformin hydrochloride (500 mg/tablet) of 0.1mg/mL (100mg/L) was measured under the same experimental conditions-5A, the standard curve equation is used for calculating the concentration of the sample to be 0.1010mg/mL, and the content of each tablet of medicine to be 505 mg. The average recovery rate of metformin hydrochloride content in the same batch of samples measured 10 times is 103.5%, and the relative standard deviation RSD value is 4.2%.
The invention utilizes the good conductivity of the conductive glass electrode and combines the properties of N-N dimethylformamide and silver nitrate to prepare the electrode with high sensitivity to the metformin hydrochloride. Then, by optimizing the parameters of N-N dimethylformamide such as the number of scanning circles, the type of buffer solution, the scanning speed, the pH value of base solution and the like, the electrochemical analysis method which has higher selectivity and higher sensitivity to N-N dimethylformamide and is easier to operate is obtained, and the method is applied to the determination of actual samples.
Claims (2)
1. An electrode for measuring metformin hydrochloride is characterized in that the electrode is an N-N dimethylformamide/nano-silver modified conductive glass electrode, wherein the N-N dimethylformamide/nano-silver modified conductive glass electrode is a three-electrode system consisting of a working electrode, a platinum electrode and a saturated calomel electrode as reference electrodes;
the preparation method comprises the following steps: placing a three-electrode system consisting of a base electrode made of conductive glass as a working electrode, a platinum wire electrode as a counter electrode and a saturated calomel electrode as a reference electrode in N-N dimethylformamide; circularly scanning for 5 weeks at a sweeping speed of 100mV/s between 0-1V potential ranges until the cyclic voltammetry curve is stable; taking out the electrode, placing the electrode in a silver nitrate solution of 5mmol/L under a static condition, and in a potential range of-0.2 to-0.8V, wherein the linear dissolution sweep rate is 0.5mV/s, and the dissolution time is 180s, and finally obtaining the N-N dimethylformamide/nano silver modified conductive glass electrode.
2. A method for measuring metformin hydrochloride using the electrode for measuring metformin hydrochloride according to claim 1, wherein the measuring method comprises:
the N-N dimethylformamide/nano silver electrode system is placed in a metformin hydrochloride standard solution with the concentration of 0.075-0.2 mg/mL, PBS with the pH value of 6.64 is used as a buffer solution, and the content of the metformin hydrochloride is measured under the conditions that the potential range is 0-1V and the scanning speed is 50 mV/s.
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| CN103852499A (en) * | 2012-11-29 | 2014-06-11 | 北京市药品检验所 | Method used for rapid detection of illegally added biguanide compound in product |
| CN106596663A (en) * | 2016-12-10 | 2017-04-26 | 武汉市农业科学技术研究院农业环境安全检测研究所 | Method for rapidly detecting metformin hydrochloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103852499A (en) * | 2012-11-29 | 2014-06-11 | 北京市药品检验所 | Method used for rapid detection of illegally added biguanide compound in product |
| CN106596663A (en) * | 2016-12-10 | 2017-04-26 | 武汉市农业科学技术研究院农业环境安全检测研究所 | Method for rapidly detecting metformin hydrochloride |
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