CN111272842B - Polyaniline modified electrode capable of quantitatively detecting estrone and preparation method and application thereof - Google Patents
Polyaniline modified electrode capable of quantitatively detecting estrone and preparation method and application thereof Download PDFInfo
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- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 title claims abstract description 92
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 title claims abstract description 92
- 229960003399 estrone Drugs 0.000 title claims abstract description 92
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000835 electrochemical detection Methods 0.000 claims abstract description 12
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- 239000000463 material Substances 0.000 claims description 40
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- BFPYWIDHMRZLRN-SLHNCBLASA-N Ethinyl estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 BFPYWIDHMRZLRN-SLHNCBLASA-N 0.000 description 1
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- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention relates to the technical field of electrochemical detection, and particularly discloses a polyaniline modified electrode for quantitatively detecting estrone, and a preparation method and application thereof. The preparation method of the polyaniline modified electrode comprises the following steps: (1) preparing polyaniline; (2) and (2) modifying the polyaniline prepared in the step (1) on a glassy carbon electrode to obtain the polyaniline modified electrode. The electrochemical device consisting of the polyaniline modified electrode prepared by the invention can realize the quantitative detection of estrone, has the advantages of simple operation, low cost, wide detection range, low detection limit and the like, and has wide application prospects in the aspects of clinical diagnosis, auxiliary treatment, drug research and development and the like.
Description
Technical Field
The invention relates to the technical field of electrochemical detection, in particular to a polyaniline modified electrode for quantitatively detecting estrone and a preparation method and application thereof.
Background
Estrone, also called female ketone, is an original hormone secreted by ovaries of female animals, is also an important medical intermediate, and can be used for synthesizing a series of estrogen medicines such as estradiol, ethinyl estradiol ether and the like. Estrone has an important effect on maintaining the normal pregnancy function of women, and is mainly used for treating uterine hypoplasia, menstrual disorder, climacteric disturbance and the like clinically. Estrone is an indispensable body hormone for women, and has important significance in aspects such as clinical diagnosis, auxiliary treatment, drug research and development and the like when being quantitatively detected. At present, the estrone has breakthrough in the aspects of chemical synthesis and medical research, but the estrone is almost insoluble in water, and few reports are made on a method for measuring the content of the estrone. The traditional method for detecting estrone is mainly high performance liquid chromatography, but the method has the defects of complicated detection steps, higher cost, low efficiency, incapability of keeping pace with the modern rapid production and inconvenience for the development of quality control production of pharmaceutical enterprises. At present, electrochemical detection methods are attracting much attention due to their advantages of convenient operation, high sensitivity, short detection time, and the like. In the construction process of the electrochemical detection method, because the bare electrode has low electrocatalytic activity and weak electrochemical response to an analyte, the key for developing the electrochemical detection method is to prepare an electrode material with excellent electrocatalytic performance so as to improve the electrochemical response performance of the working electrode. Nevertheless, electrode modification materials reported to enhance the electrochemical response signal of estrone are also very limited. In order to solve the existing problems, the invention provides the polyaniline modified electrode for quantitatively detecting estrone, and the electrode has the advantages of simple preparation, low cost, wide detection range, low detection limit and the like.
Disclosure of Invention
The invention provides a preparation method of a polyaniline modified material and an estrone detection method, aiming at solving the problems of complicated detection steps, higher cost and low efficiency in the prior art for detecting estrone; the modified electrode prepared from the material has a wider detection range and a lower detection limit when being used for detecting estrone.
Another technical problem to be solved by the present invention is to provide a polyaniline-modified electrode.
The invention also aims to solve the technical problem of providing the application of the polyaniline modified electrode in detecting the content of estrone in a medicine.
The technical problem to be solved by the invention is realized by the following technical scheme:
a preparation method of a polyaniline modified material comprises the following steps:
(1) preparation of aniline solution and potassium peroxodisulfate solution: adding 50-60 mL of 4-6 mol/L sulfuric acid into 2-3 mL of aniline to prepare aniline solution; adding 50-70 mL of 4-6 mol/L sulfuric acid into 3-4 g of potassium peroxodisulfate to prepare a potassium peroxodisulfate solution;
(2) cooling the aniline solution prepared in the step (1) to-15 to-20 ℃, and then dropwise adding a potassium peroxodisulfate solution into the aniline solution; and after the dropwise addition is finished, magnetically stirring for 20-40 seconds, reacting for 16-30 hours at the temperature of-15 to-20 ℃, and separating, washing and drying a product to obtain the polyaniline modified material.
Preferably, step (1) is specifically: adding 57-58 mL of 4.5-5.5 mol/L sulfuric acid into 2.2-2.5 mL of aniline to prepare aniline solution; adding 55-65 mL of 4.5-5.5 mol/L sulfuric acid into 3.4-3.6 g of potassium peroxodisulfate to prepare a potassium peroxodisulfate solution.
Most preferably, step (1) is specifically: adding 57.6mL of 5mol/L sulfuric acid into 2.4mL of aniline to prepare an aniline solution; to 3.55g of potassium peroxodisulfate was added 60mL of 5mol/L sulfuric acid to prepare a potassium peroxodisulfate solution.
Preferably, the step (2) is specifically: cooling the aniline solution prepared in the step (1) to-16 to-18 ℃, and then dropwise adding a potassium peroxodisulfate solution into the aniline solution; after the dropwise addition is finished, magnetically stirring for 30-40 seconds, reacting for 24-30 hours at the temperature of-16 to-18 ℃, and separating, washing and drying a product to obtain the polyaniline modified material;
most preferably, step (2) is specifically: cooling the aniline solution prepared in the step (1) to-17 ℃, and then dropwise adding a potassium peroxodisulfate solution into the aniline solution; and after the dropwise addition is finished, magnetically stirring for 30 seconds, reacting for 24 hours at the temperature of minus 17 ℃, and separating, washing and drying the product to obtain the polyaniline modified material.
Preferably, the washing in step (2) is performed by first using a NaOH solution and then using deionized water.
The invention also provides the polyaniline modified material prepared by the preparation method.
For preparing an electrode for determining the content of a specific chemical component or substance using a chemically modified material, the inventors were required to prepare different chemically modified electrode materials according to the properties of the specific chemical component or substance to be determined. The quality of the detection range, detection limit, sensitivity, stability, anti-interference and other effects of the prepared modified electrode on the substance to be detected is mainly determined by the preparation method of the chemical modified material. The preparation method of the chemical modification material mainly comprises the selection of raw materials, the proportion of the raw materials, the reaction conditions of each step and the like. For the modified material used as the electrode, the selection and the proportion of raw materials in the preparation method and the difference of reaction conditions in each step can cause the great difference of the electrochemical performance of the electrode obtained by subsequent preparation, thereby causing the great difference of the effects of detection range, detection limit, sensitivity, stability, anti-interference performance and the like.
According to the characteristics of the estrone, in order to obtain the estrone detection electrode with a wide detection range and a low detection limit, the inventor of the invention continuously adjusts the raw material composition, the proportion and the process parameters in the preparation process through a large number of experiments to prepare a brand-new polyaniline material, and further prepares a polyaniline modified electrode; the polyaniline prepared by the method has a sheet structure similar to graphene, and also has three-dimensional porous gaps, which is beneficial to enrichment and transmission of analysis substances on the surface of an electrode. Based on the structural advantages, the invention can effectively improve the catalytic performance and the stability of the prepared chemically modified electrode, increase the detection range of estrone and simultaneously reduce the detection limit of estrone.
The invention also provides a preparation method of the polyaniline modified electrode for quantitatively detecting estrone, which comprises the following steps:
(1) ultrasonically dispersing 0.5-1 mg of the polyaniline-modified material according to claim 5 in 0.5-1 mL of N, N-dimethylformamide solvent to obtain a polyaniline-modified liquid;
(2) dropwise adding the polyaniline modified solution on the surface of the pretreated glassy carbon electrode, and drying to obtain a polyaniline modified electrode capable of being used for quantitatively detecting estrone;
the invention also provides a polyaniline modified electrode which is prepared by the method and can be used for quantitatively detecting estrone.
The invention also provides an application of the modified electrode for quantitatively detecting the content of the estrone in the medicine, wherein the polyaniline modified electrode for quantitatively detecting the estrone is used as a working electrode, a platinum wire electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode to form a three-electrode system, and the three-electrode system is assembled and then connected with an electrochemical workstation to form an electrochemical detection device; the measurement is carried out by adopting differential pulse voltammetry:
the differential pulse voltammetry is adopted, and the method specifically comprises the following steps:
preparing a standard solution and a sample solution to be detected;
measuring oxidation peak current values corresponding to the estrone standard solutions with different concentrations by using a differential pulse voltammetry method to obtain a linear range and a linear equation of the estrone concentration and the oxidation peak current response value thereof; then measuring the oxidation peak current response value of the sample solution to be measured, and converting out the concentration of the estrone according to a linear equation so as to obtain the content of the estrone in the sample;
the operating conditions of the differential pulse voltammetry are as follows: the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s.
Preferably, the linear range and the linear equation are as follows: the linear equation is i in the range of 4.0-100.0 mu mol/L p (A)＝0.03334c(mol/L)-5.1212×10 -8 (R 2 0.9832), linear equation i in the range of 100.0 to 7000.0 mu mol/L p (A)＝0.00326c(mol/L)+2.8900×10 -6 (R 2 0.9919); in the equation, c is the concentration of estrone, i p Obtaining a current response value for the differential pulse voltammetry;
preferably, the standard solution and the sample solution to be detected are prepared by absolute ethyl alcohol containing 0.2-0.27 g/L NaOH.
Estrone is insoluble in water (only soluble in some organic solvents, but the organic solvents are not conductive), and water commonly used in an electrochemical detection method is used as a solvent to prepare various detection base solutions, so that the development of an estrone electrode is limited; the research of the invention finds that the base solution containing NaOH absolute ethyl alcohol can dissolve estrone and increase the conductivity; the base solution containing NaOH absolute ethyl alcohol is matched with the electrode, so that the optimal detection effect can be obtained.
Has the advantages that: (1) in order to overcome the defects that the preparation process of the existing modified material is relatively complex, the cost is relatively high, the film forming property and the stability of the prepared material are poor and the like, the invention provides a polyaniline modified electrode which can be used for quantitatively detecting estrone and an electrochemical detection device comprising the electrode; (2) with graphene or MnO commonly used as electrode modification material 2 Compared with the material, the polyaniline can effectively improve the electrocatalytic activity of the modified electrode on estrone; (3) the detection range of the polyaniline modified electrode for quantitatively detecting estrone is 4.0-7000.0 mu mol/L, the detection limit is 0.52 mu mol/L, and the sensitivity is 0.03334A/(mol/L); (4) the electrode has strong anti-interference performance, and experiments prove that substances such as folic acid, urea, dichlorophen, manganese sulfate and palladium chloride with the concentration of 10 times, 5-hydroxytryptamine with the concentration of 1 time and the like do not influence the detection of estrone; (5) the electrode has good stability, and the current response value of the electrode is still more than 90% of the initial value after the electrode is kept for 30 days at room temperature. The chemically modified electrode prepared by the invention and the electrochemical detection device composed of the chemically modified electrode can realize quantitative detection of estrone in medicines, and have the advantages of simple operation, high sensitivity, low detection limit, low cost and the like.
Drawings
Fig. 1 is a scanning electron micrograph (a), an energy spectrum (B) and an infrared spectrum (C) of the polyaniline-modified material.
FIG. 2 glassy carbon electrode (a), MnO 2 And (c) a cyclic voltammogram (A) and a differential pulse voltammogram (B) of the modified electrode (B), the graphene modified electrode (c) and the polyaniline modified electrode (d) in an ethanol base solution containing 7.0mmol/L of estrone.
FIG. 3 is a cyclic voltammogram of a polyaniline-modified electrode in an ethanol base solution containing 7.0mmol/L estrone at different NaOH dosages.
FIG. 4 is a graph (A) of cyclic voltammograms and a relationship (B) of enrichment potential to peak current of a polyaniline-modified electrode in an ethanol base solution containing 7.0mmol/L estrone at different enrichment potentials; and a cyclic voltammogram (C) and a graph (D) of the relationship between enrichment time and peak current under different enrichment time conditions.
FIG. 5 is a differential pulse voltammogram (A) of estrone on polyaniline modified electrode with different concentrations and a linear relationship graph (B) between the concentration of estrone and its peak current value.
Detailed Description
The present invention will be further explained with reference to specific examples, which are not intended to limit the present invention in any way.
Example 1 preparation of polyaniline-modified material
(1) Preparation of aniline solution and potassium peroxodisulfate solution: adding 57.6mL of 5mol/L sulfuric acid into 2.4mL of aniline to prepare an aniline solution; adding 60mL of 5mol/L sulfuric acid into 3.55g of potassium peroxodisulfate to prepare a potassium peroxodisulfate solution;
(2) cooling the aniline solution prepared in the step (1) to-17 ℃, and then dropwise adding a potassium peroxodisulfate solution into the aniline solution; and after the dropwise addition is finished, magnetically stirring for 30 seconds, reacting for 24 hours at the temperature of minus 17 ℃, filtering to obtain a precipitate, washing the precipitate with a 1mol/L NaOH solution, washing the product with deionized water for multiple times, and naturally airing the product at room temperature to obtain the polyaniline modified material.
Fig. 1 is a scanning electron micrograph (a), an energy spectrum (B) and an infrared spectrum (C) of the polyaniline-modified material. From fig. 1(a), it can be seen that the polyaniline modified material prepared by the method has a sheet structure similar to graphene, and a three-dimensional porous gap structure is formed by connecting sheets, so that the structural characteristics are favorable for the enrichment and transmission of analysis substances on the surface of an electrode, the specific surface area of the modified electrode can be increased, the electrocatalytic activity of the modified electrode can be improved, and the sensing performance and the stability of the modified electrode can be enhanced. As shown in fig. 2, the polyaniline-modified material prepared by the present invention mainly contains C, O, S elements. As can be seen from FIG. 3, the polyaniline-modified material prepared by the invention is 1556cm -1 、 1442cm -1 、1245cm -1 And 1168cm -1 Respectively, obvious absorption peaks appear, which respectively correspond to the stretching or bending vibration of the N, -N, C-N and the benzene ring; at the same time at 1020cm -1 The stretching vibration absorption peak of-N-also appears, and the characteristic peak confirms the successful synthesis of the polyaniline modified material.
Example 2 preparation of polyaniline-modified electrode for quantitative determination of estrone
Using 0.3 μm and 0.05 μm Al 2 O 3 Polishing and grinding a glassy carbon electrode (GCE, the diameter of which is 3mm) on abrasive paper into a smooth mirror surface, and then sequentially ultrasonically cleaning the GCE for 10min by using dilute nitric acid, acetone and distilled water in a ratio of 1:1 to obtain the pretreated glassy carbon electrode. Then, 0.5mg of the polyaniline-modified material prepared in example 1 was put into a centrifuge tube, 0.5mL of N, N-Dimethylformamide (DMF) solution was added, and the polyaniline-modified solution was obtained by ultrasonic dispersion for 10 minutes. 0.05 mu L of polyaniline modified liquid is uniformly dripped on the surface of a pretreated glassy carbon electrode, a layer of black film is formed by drying and is adsorbed on the glassy carbon electrode, and the polyaniline modified electrode (referred to as polyaniline modified electrode for short) for quantitatively detecting estrone is obtained, and before the polyaniline modified electrode is used, the polyaniline modified electrode needs to be scanned for 6 times between-1.0V and 1.0V in the liquid to be detected by a cyclic voltammetry method so as to activate the electrode.
For ease of comparison, MnO was used in accordance with the above method 2 Preparing MnO by using graphene instead of polyaniline modified material 2 Modified electrode and graphite alkene modified electrode.
Example 3 detection Properties of polyaniline-modified electrode
In this example, each modified electrode prepared in example 2 was used as an experimental object, and a platinum wire counter electrode and a saturated calomel reference electrode were combined to form a three-electrode system, which was connected to a CHI660 electrochemical workstation (shanghai chenhua instruments ltd) to perform electrochemical performance detection.
(1) Comparison of electrocatalytic oxidation performance of estrone by different electrodes
FIG. 2 glassy carbon electrode (a), MnO 2 The content of the modified electrode (b), the graphene modified electrode (c) and the polyaniline modified electrode (d) is 7.0mmol/LCyclic voltammogram (A) and differential pulse voltammogram (B) in the estrone ethanol base solution. As can be seen from FIG. 2A, the estrone showed a weak oxidation peak on the bare glassy carbon electrode, while the estrone oxidation peak was more pronounced on the modified electrode. The oxidation peak current on the polyaniline modified electrode is the largest, which shows that polyaniline has the best electrocatalytic oxidation effect on estrone, and is beneficial to improving the detection performance of the sensor prepared from the polyaniline. As shown in FIG. 2B, estrone showed the largest peak current at the polyaniline-modified electrode of about 27 μ A, while it was only 5 μ A at the glassy carbon electrode and MnO at the glassy carbon electrode 2 The modified electrode is about 10 muA, and the graphene modified electrode is about 13 muA. Compared with other electrodes, the polyaniline modified electrode has the largest increase of current response amplitude, which shows that the polyaniline modified electrode has the best detection sensitivity on the estrone and is beneficial to improving the detection range and detection limit of the electrode on the estrone. In addition, the peak shape of the estrone on the polyaniline modified electrode is the best, which shows that the quantitative detection of the estrone by using the polyaniline modified electrode has a better detection signal.
The operating conditions set by the cyclic voltammetry are as follows: the sweeping speed is 0.05V/s; the potential range is-0.4 to 1.0V.
The detection conditions of the differential pulse voltammetry are as follows: the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s.
(2) The polyaniline modified electrode prepared by the method has electrochemical response performance to estrone under the condition of different NaOH dosage in ethanol base solution
The change situation of the oxidation peak current of 7.0mmol/L estrone in supporting electrolyte with different NaOH dosages in ethanol base solution is examined by using a differential pulse voltammetry method in a three-electrode system taking the polyaniline modified electrode prepared in the embodiment 2 as a working electrode (the estrone is insoluble in water and is prepared by using absolute ethanol of test solution, and the absolute ethanol is almost non-conductive, so that the conductivity of the test solution is increased by adding flaky sodium hydroxide), and the results show that (shown in figure 3A) the estrone in the ethanol base solution without NaOH has small oxidation peak and poor peak shape, and the ethanol base solution with 0.023-0.267 g/L NaOH has obvious oxidation peak, and the peak current is increased and then decreased along with the increase of the NaOH dosage. This is probably because the conductivity of the base solution is low and the peak current is low due to the too small amount of sodium hydroxide; too much sodium hydroxide may destroy the stability of the estrone solution and the peak current is low. As can be seen from FIG. 3B, the electrode prepared by the present invention has the best electrochemical detection effect on estrone under the condition that the amount of NaOH in the ethanol base solution is 0.2 g/L.
The detection conditions of the differential pulse voltammetry are as follows: the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s.
(3) The polyaniline modified electrode prepared by the invention has electrochemical response performance to estrone under different enrichment conditions
In a three-electrode system using the polyaniline material modified electrode prepared in this embodiment 2 as a working electrode, differential pulse voltammetry scanning is performed in an estrone ethanol base solution with a concentration of 7.0mmol/L, as shown in fig. 4A, first, the deposition time is kept unchanged, the deposition potential is changed, and data of different enrichment potentials are recorded and compared. As can be seen from fig. 4B, when the accumulation potential is 0.2V, the peak current is the highest, and the peak shape is better, which is the optimal accumulation potential. The enrichment potential was then held constant at 0.2V and the deposition time was increased by 30s each time, as shown in fig. 4C, and data was recorded and compared for different enrichment times. As can be seen from fig. 4D, when the enrichment time is increased from 0s to 150s, the peak current increases to the maximum, and the peak current measured after 150s for every 30s of enrichment time still increases, but the increase is not large, and 150s is finally selected as the optimal enrichment time to improve the efficiency of the experiment.
The detection conditions of the differential pulse voltammetry are as follows: the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s.
(4) The polyaniline modified electrode prepared by the invention has electrochemical detection performance on estrone
Prepared as in example 2In a three-electrode system with a polyaniline modified electrode as a working electrode, absolute ethyl alcohol containing 0.2g/L NaOH is used as supporting electrolyte, differential pulse voltammetry scanning is carried out on a series of concentrations of estrone solution, and the result shows that (shown in figure 5) the oxidation peak current of estrone increases along with the increase of the concentration, and good two-stage linear relation appears in the concentration range of 4.0-7000.0 mu mol/L, wherein the linear equation in the range of 4.0-100.0 mu mol/L is i p (A)＝0.03334c(mol/L)-5.1212×10 -8 (R 2 0.9832) and a linear equation of i in the range of 100.0 to 7000.0 [ mu ] mol/L p (A)＝0.00326c(mol/L) +2.8900×10 -6 (R 2 0.9919); in the equation, c is the concentration of estrone, i p Current response values were obtained for differential pulse voltammetry. From the triple signal-to-noise ratio, the detection limit was calculated to be 0.52. mu. mol/L, and the sensitivity was 0.03334A/(mol/L). The electric sensor constructed by the prepared modified electrode has good linear relation, high sensitivity and low detection limit.
The detection conditions of the differential pulse voltammetry are as follows: the enrichment potential is 0.2V, the enrichment time is 150s, the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s.
(5) The anti-interference capability and stability of the polyaniline modified electrode prepared by the invention are improved.
In a three-electrode system using the polyaniline modified electrode prepared in this example 2 as a working electrode, absolute ethyl alcohol containing 0.2g/L NaOH is used as a supporting electrolyte, and the influence of common interfering substances on the oxidation peak current of estrone is examined by using differential pulse voltammetry. The allowable test error is controlled to be +/-5%, and the result shows that substances such as folic acid, urea, dichlorophen, manganese sulfate and palladium chloride with the concentration being 10 times that of the polyaniline modified electrode prepared by the method, 5-hydroxytryptamine with the concentration being 1 time that of the polyaniline modified electrode and the like do not influence the determination of estrone, so that the electrode prepared by the method has excellent selectivity and can be used for detecting estrone in an actual sample.
And (3) observing the stability of the polyaniline modified electrode by using a differential pulse voltammetry method. Firstly, the prepared electrode, a three-electrode system consisting of a platinum wire electrode and a saturated calomel electrode are connected with an electrochemical workstation, and the oxidation peak current initial value of 7.0mmol/L estrone is measured in absolute ethyl alcohol containing 0.2g/L NaOH as supporting electrolyte. The peak current value of the electrode can reach more than 90% of the initial value by measuring the estrone with the same concentration under the same condition within one month after the electrode is stored at room temperature, and the electrode prepared by the invention is proved to have good storage stability.
The detection conditions of the differential pulse voltammetry are as follows: the enrichment potential is 0.2V, the enrichment time is 150s, the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s.
EXAMPLE 4 method for measuring estrone content in actual sample
(1) A polyaniline material modified electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode to form a three-electrode system, and the three-electrode system is connected to an electrochemical workstation;
(2) preparing a solution to be detected of an actual sample;
(3) the oxidation peak current value of the estrone in the solution to be tested of the actual sample is measured by differential pulse voltammetry, and the concentration of the estrone is calculated according to a linear relation chart or a linear equation (as described in example 3) shown in fig. 5.
The detection conditions of the differential pulse voltammetry are as follows: the enrichment potential is 0.2V, the enrichment time is 150s, the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s.
EXAMPLE 5 measurement of estrone content in actual sample
One tablet (0.4mg) of folic acid tablets of a certain brand medicine is taken, 20mL of absolute ethyl alcohol is added for soaking for 24 hours, then 10mL of solution is taken, and sodium hydroxide is added for dissolution to be used as an actual sample solution to be detected (the concentration of the sodium hydroxide in the actual sample solution to be detected is 0.2 g/L). A polyaniline modified electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode to form a three-electrode system, and the three-electrode system is connected to an electrochemical workstation; and measuring the content of the estrone in the sample liquid by using a differential pulse voltammetry method. The detection conditions of the differential pulse voltammetry are as follows: the enrichment potential is 0.2V, the enrichment time is 150s, the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s. Measuring the oxidation peak current value of estrone by differential pulse voltammetry; then 0.1mL of 1.8mmol/L estrone standard solution (sequentially added for three times for measurement) is taken and sequentially added into an actual sample for differential pulse voltammetry determination. The corresponding concentration value of estrone in the measured sample is found according to the linear relation graph or linear equation (described in example 3) shown in the figure 4 and the oxidation peak current value in the obtained differential pulse voltammogram. According to the detection method, the content of estrone in the folic acid tablets is 18.2 mu mol/L, and the average recovery rate is 98.7%.
Claims (8)
1. The application of the modified electrode capable of being used for quantitatively detecting the content of the estrone in the medicine is characterized in that a polyaniline modified electrode capable of being used for quantitatively detecting the estrone is used as a working electrode, a platinum wire electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode to form a three-electrode system, and the three-electrode system is assembled and then connected with an electrochemical workstation to form an electrochemical detection device; the measurement is carried out by adopting differential pulse voltammetry:
the differential pulse voltammetry is adopted, and the method specifically comprises the following steps:
preparing a standard solution and a sample solution to be detected;
measuring oxidation peak current values corresponding to the estrone standard solutions with different concentrations by using a differential pulse voltammetry method to obtain a linear range and a linear equation of the estrone concentration and the oxidation peak current response value thereof; then measuring the oxidation peak current response value of the sample solution to be measured, and converting out the concentration of the estrone according to a linear equation so as to obtain the content of the estrone in the sample;
the operating conditions of the differential pulse voltammetry are as follows: the potential range is-0.4-1.0V, the potential increment is 4mV, the amplitude is 50mV, the primary pulse width is 0.2s, the secondary pulse width is 0.05s, the sample measuring width is 0.0167s, and the pulse period is 0.5 s;
the preparation method of the polyaniline modified electrode for quantitatively detecting estrone comprises the following steps:
(1) carrying out ultrasonic dispersion on 0.5-1 mg of polyaniline modified material in 0.5-1 mL of N, N-dimethylformamide solvent to obtain polyaniline modified liquid;
(2) dropwise adding the polyaniline modified solution on the surface of the pretreated glassy carbon electrode, and drying to obtain a polyaniline modified electrode capable of being used for quantitatively detecting estrone;
the preparation method of the polyaniline modified material comprises the following steps:
(1) preparation of aniline solution and potassium peroxodisulfate solution: adding 50-60 mL of 4-6 mol/L sulfuric acid into 2-3 mL of aniline to prepare aniline solution; adding 50-70 mL of 4-6 mol/L sulfuric acid into 3-4 g of potassium peroxodisulfate to prepare a potassium peroxodisulfate solution;
(2) cooling the aniline solution prepared in the step (1) to-15 to-20 ℃, and then dropwise adding a potassium peroxodisulfate solution into the aniline solution; and after the dropwise addition, magnetically stirring for 20-40 seconds, reacting for 16-30 hours at-15 to-20 ℃, separating, washing and drying the product to obtain the polyaniline modified material.
2. The application of claim 1, wherein the step (1) in the preparation method of the polyaniline-modified material is specifically as follows: adding 57-58 mL of 4.5-5.5 mol/L sulfuric acid into 2.2-2.5 mL of aniline to prepare aniline solution; adding 55-65 mL of 4.5-5.5 mol/L sulfuric acid into 3.4-3.6 g of potassium peroxodisulfate to prepare a potassium peroxodisulfate solution.
3. The application of claim 2, wherein the step (1) in the preparation method of the polyaniline-modified material is specifically as follows: adding 57.6mL of 5mol/L sulfuric acid into 2.4mL of aniline to prepare an aniline solution; to 3.55g of potassium peroxodisulfate was added 60mL of 5mol/L sulfuric acid to prepare a potassium peroxodisulfate solution.
4. The application of claim 1, wherein the step (2) in the preparation method of the polyaniline-modified material is specifically as follows: cooling the aniline solution prepared in the step (1) to-16 to-18 ℃, and then dropwise adding a potassium peroxodisulfate solution into the aniline solution; and after the dropwise addition, magnetically stirring for 30-40 seconds, reacting for 24-30 hours at-16 to-18 ℃, separating, washing and drying the product to obtain the polyaniline modified material.
5. The application of claim 4, wherein the step (2) in the preparation method of the polyaniline-modified material is specifically as follows: cooling the aniline solution prepared in the step (1) to-17 ℃, and then dropwise adding a potassium peroxodisulfate solution into the aniline solution; and after the dropwise addition is finished, magnetically stirring for 30 seconds, reacting for 24 hours at the temperature of minus 17 ℃, and separating, washing and drying the product to obtain the polyaniline modified material.
6. The use according to claim 1, wherein the washing in step (2) of the preparation method of the polyaniline-modified material is performed by first washing with NaOH solution and then with deionized water.
7. The use of claim 1, wherein the linear range and linear equation are: the linear equation is ip = 0.03334 c-5.1212 x 10-8 in the range of 4.0-100.0 mu mol/L, R2 = 0.9832, the linear equation is ip = 0.00326 c + 2.8900 x 10-6 in the range of 100.0-7000.0 mu mol/L, and R2 = 0.9919; in the equation, c is the concentration of estrone and the unit is mol/L; i p is differential pulse voltammetry to obtain current response value with unit of A.
8. The application of claim 1, wherein the standard solution and the sample solution to be tested are prepared by using absolute ethyl alcohol containing 0.2-0.27 g/L NaOH.
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Application publication date: 20200612 Assignee: Hunan Songyitang Technology Co.,Ltd. Assignor: Hengyang Normal University Contract record no.: X2023980047920 Denomination of invention: Polyaniline modified electrode for quantitative detection of estrone and its preparation method and application Granted publication date: 20220930 License type: Common License Record date: 20231123 |
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