CN113433181A - Electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin - Google Patents
Electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin Download PDFInfo
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Abstract
The invention discloses an electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin. The phosphorus-doped hierarchical porous carbon nanosphere is synthesized by using xylan as a carbon source and polyvinylpyrrolidone as a structure directing agent through a hydrothermal method in combination with phosphoric acid activation. The phosphorus-doped hierarchical porous carbon nanosphere modified glassy carbon electrode is used for carrying out electrochemical detection, the modified electrode shows good electrocatalytic activity and oxidase-like reaction on luteolin and baicalin, and compared with the traditional voltammetry, the first-order derivative voltammetry realizes the distinguishable detection of two flavone compounds. The sensor prepared by the invention has the advantages of low preparation cost of sensor materials, simple operation, high speed and efficiency, strong selectivity, high sensitivity and the like, and solves the problem that two flavone compounds can be difficult to distinguish and detect simultaneously.
Description
Technical Field
The invention relates to the technical field of electrochemical sensing, in particular to an electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin.
Background
Luteolin and baicalin are widely present in plants, vegetables and fruits as representative flavonoids. They have received a great deal of attention in clinical and pharmaceutical fields because of their various biological activities and pharmacological effects (antioxidant, anti-inflammatory, antiallergic, and anticancer activities) on human health. Based on the pharmacological actions, different kinds of concentrated compound herbal preparations containing luteolin and baicalin as active ingredients are clinically used. To date, several analytical methods have been reported for luteolin or baicalin, such as High Performance Liquid Chromatography (HPLC), Capillary Electrophoresis (CE), spectrophotometry, and liquid chromatography-mass spectrometry (LC-MS). Although these methods have the advantage of sensitivity and accuracy, they have many of their own drawbacks, such as being time consuming, costly or complicated to operate. Therefore, the establishment of a method for rapidly, efficiently and distinguishably measuring luteolin and baicalin has important significance.
The electrochemical sensing technology has attracted extensive attention in the analysis of flavonoid compounds due to the advantages of high sensitivity, high accuracy, simple and convenient field measurement and the like. Luteolin and baicalin have been applied to the analysis and detection of electrochemical sensing based on their electrical activity containing phenolic hydroxyl groups. For example, Liao et al (Y Liao, N Wang, Y Ni, J Xu and S Shao, Journal of electrochemical Chemistry,2015,754:94-99) modified glassy carbon electrode with nitro group substituted 3,3 '-bis (indolyl) methane (Nbiim)/Carbon Nanotubes (CNT) combined with Nbiim' S selective adsorption of flavonoids and the unique properties of CNTs, achieved efficient assay of luteolin with a linear relationship in the concentration range of 5-320nM with a detection limit of 0.6 nM. Similarly, the measurement of luteolin by Tang et al (J Tang, R Huang, S B Zheng, S X Jiang, H Yu, Z R Li and J F Wang, Microchemical Journal,2019,145: 899-. In the report of baicalin determination, early Wang et al (F Wang, M X Lv, K Lu, L G and J Liu, Journal of China Chemical Society,2012,59: 829-. Then, the molybdenum disulfide (MoS2) nano-sheet modified electrode (MoS2/GCE) prepared by Zhang et al (HYZhang, TYWang, YL Qiu, F Fu and Y Y Yu, Journal of electrochemical Chemistry,2016,775: 286-. By combining the reports, the carbon materials are complex in preparation process, high in detection limit of modified electrodes, low in efficiency and not beneficial to popularization, and only can be detected by a single flavonoid compound. Therefore, it remains a challenge to construct electrode materials with high electrocatalytic performance and selectivity for simultaneous analysis of multiple flavonoids.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the electrochemical sensing method for simultaneously distinguishing and detecting the luteolin and the baicalin, which has the advantages of compact structure, reduced working strength of workers, improved filtrate filtration efficiency, improved medicine component extraction efficiency and simple operation.
The purpose of the invention is realized by the following technical scheme: an electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin comprises the steps of taking a phosphorus-doped hierarchical porous carbon nanosphere modified electrode as a working electrode, measuring the content of luteolin and baicalin in a solution by using a differential pulse voltammetry, and carrying out first-order derivative voltammetry treatment on obtained data.
An electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin comprises the following steps:
step 1: preparation of the modifying Material
The preparation method comprises the steps of taking xylan with a certain mass as a carbon source, introducing polyvinylpyrrolidone with a certain mass and sulfuric acid with a certain volume, carrying out hydrothermal reaction for a certain time at a certain temperature to obtain a precursor, carrying out centrifugal cleaning with ethanol and water to obtain the precursor, activating the dried precursor and phosphoric acid according to a certain proportion, and finally calcining in a tubular furnace under the protection of inert gas to prepare the phosphorus-doped hierarchical porous carbon nanospheres.
Step 2: preparation of modified electrode
After the phosphorus-doped hierarchical porous carbon nanospheres and ultrapure water are subjected to ultrasonic dispersion according to the proportion of 1mg/mL, 5 mu L of dispersion liquid is dripped on the glassy carbon electrode and dried to prepare the phosphorus-doped hierarchical porous carbon nanosphere modified electrode.
In the step 1, the mass of xylan is 1g, the mass of polyvinylpyrrolidone is 0.3g, the volume of sulfuric acid is 1mL, and the concentration of xylan is 95%.
In the step 1, the hydrothermal reaction temperature is 433K, and the reaction time is 4 h.
In the step 1, the ratio of the precursor to the phosphoric acid is 1:4, and the inert gas is N2.
In the step 2, a traditional three-electrode system is formed by taking a phosphorus-doped hierarchical porous carbon nanosphere modified electrode as a working electrode, a platinum wire electrode as a counter electrode and a reference electrode as a saturated calomel electrode, and a phosphate buffer solution is taken as an electrolyte solution. In the step 2, the pH of the phosphate buffer solution is 2, and the concentration is 0.1M.
The invention has the following advantages:
1. the carbon source adopted by the invention is xylan (95 percent) which comes from natural plants and has strong reproducibility, the preparation cost is low, the process is simple, and the phosphoric acid has the activation and doping effects at the same time.
2. The electrochemical sensor prepared by the invention not only can selectively detect luteolin or baicalin, but also has strong distinguishability and wide detection concentration range when being used for simultaneous determination, the detection limits of luteolin and baicalin are 0.38nM and 2.16nM respectively, and the electrochemical sensor has good stability, reproducibility and anti-interference performance, and can be used for analyzing and determining luteolin and baicalin in human blood actual samples.
3. The electrochemical sensor prepared by the invention has oxidase-like characteristics when selectively measuring luteolin or baicalin and simultaneously measuring luteolin or baicalin, is different from the linear relation of the traditional modified electrode, expands the application prospect of the oxidase-like sensor, and shows obvious distinguishability and lower relative standard deviation value in actual sample analysis compared with the traditional voltammetry by using a first-order derivative voltammetry.
Drawings
FIG. 1 is a differential pulse voltammogram (A) and a first derivative voltammogram (B) of various modified electrodes of the invention in a phosphate buffer solution (0.1M, pH 2) containing both luteolin and baicalin at 6. mu.M;
FIG. 2 is a transmission electron microscope image of a phosphorus doped hierarchical porous carbon nanosphere;
in FIG. 3, A: linear scanning voltammogram of phosphorus-doped hierarchical porous carbon nanosphere modified electrodes immobilized in phosphate buffer solution (0.1M, pH 2) containing 3 μ M baicalin and containing luteolin in varying concentrations, B: in response to the relationship between current and concentration (0.01-10. mu.M), C: linear relationship of response current and low concentration (0.01-1 μ M); d: a phosphorus-doped hierarchical porous carbon nanosphere modified electrode is fixed with a linear scanning voltammogram containing 1 mu M of luteolin and baicalin with different concentrations in a phosphate buffer solution (0.1M, pH 2); e: response current vs concentration (0.01-10 μ M), F: linear relationship of response current and low concentration (0.01-1 μ M); g: the phosphorus-doped hierarchical porous carbon nanosphere modified electrode contains linear scanning voltammogram of luteolin and baicalin with different concentrations in a phosphate buffer solution (0.1M, pH 2), H: response current vs concentration (0.01-10 μ M), I: linear relationship of response current and low concentration (0.01-1 μ M); illustration is shown: the linear relation between the concentration reciprocal and the current reciprocal;
in FIG. 4; a: first derivative voltammogram of phosphorus-doped hierarchical porous carbon nanosphere modified electrode in phosphate buffer solution (0.1M, pH 2) containing 3 μ M baicalin and containing luteolin at different concentrations, B: linear relationship of response current and low concentration (0.01-1 μ M); c: first derivative voltammogram of phosphorus-doped hierarchical porous carbon nanosphere modified electrode in phosphate buffer solution (0.1M, pH 2) containing 1 μ M luteolin and different concentrations of baicalin, D: linear relationship of response current and low concentration (0.01-1 μ M); e: a first derivative voltammogram of a phosphorus-doped hierarchical porous carbon nanosphere modified electrode simultaneously containing luteolin and baicalin with different concentrations in a phosphate buffer solution (0.1M, pH 2), F: linear relationship of response current and low concentration (0.01-1 μ M);
FIG. 5 shows that the phosphorus-doped hierarchical porous carbon nanosphere modified electrode simultaneously detects the anti-interference situation of luteolin and baicalin;
FIG. 6 shows that the phosphorus-doped hierarchical porous carbon nanosphere modified electrode simultaneously detects the stability of luteolin and baicalin;
Detailed Description
The invention will be further described with reference to the accompanying drawings, without limiting the scope of the invention to the following:
example 1
An electrochemical sensing method capable of simultaneously distinguishing and detecting two flavonoid compounds luteolin and baicalin comprises the following steps:
step 1: preparation of the modifying Material
1g of xylan (95%) and 1mL of sulfuric acid were dissolved in 60mL of ultrapure water, and after ultrasonic dissolution, the resulting solution was transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene, and subjected to hydrothermal treatment at 433K for 4 hours. Naturally cooling to room temperature, filtering the obtained brown mixture to remove impurities, repeatedly carrying out high-speed centrifugal cleaning by using ultrapure water and ethanol to obtain a precursor, and drying in a 343K oven. And then, performing phosphoric acid activation treatment (the mass ratio is phosphoric acid (85%): precursor is 4:1), putting the mixture into an oven, drying the mixture at 373K, and finally calcining the mixture at 1073K for 4h at 278K/min in a tubular furnace under the protection of N2 to obtain the phosphorus-doped carbon spheres.
Step 2: preparation of modified electrode
Weighing 1mg of prepared phosphorus-doped carbon spheres, dispersing in 1mL of ultrapure water, performing ultrasonic treatment for 10 minutes to form a uniformly dispersed and stable mixed solution, dropwise coating 5 mu L of the mixed solution on the surface of a glassy carbon electrode, and drying in an infrared drying oven to obtain the phosphorus-doped carbon sphere modified electrode.
A phosphorus-doped hierarchical porous carbon nanosphere modified electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, a reference electrode is a saturated calomel electrode to form a traditional three-electrode system, a phosphate buffer solution is used as an electrolyte solution, the pH value of the phosphate buffer solution is 2, and the concentration of the phosphate buffer solution is 0.1M. The content of luteolin and baicalin in the solution is measured by using a differential pulse voltammetry method.
As shown in fig. 1A, although the prepared phosphorus-doped carbon sphere-modified electrode showed better peak response current to luteolin and baicalin than the bare electrode, it failed to form a hierarchical porous and nano-sized structure due to the lack of soft-template polyvinylpyrrolidone, thereby hindering electron transfer without using electrocatalytic oxidation of luteolin and baicalin.
Example 2
An electrochemical sensing method capable of simultaneously distinguishing and detecting two flavonoid compounds luteolin and baicalin comprises the following steps:
step 1: preparation of the modifying Material
1g of xylan (95%), 0.3g of polyvinylpyrrolidone and 1mL of sulfuric acid were dissolved in 60mL of ultrapure water, and after ultrasonic dissolution, the resulting solution was transferred to a 100mL polytetrafluoroethylene-lined stainless steel autoclave and subjected to hydrothermal treatment at 433K for 4 hours. And naturally cooling to room temperature, filtering the obtained brown mixture to remove impurities, repeatedly carrying out high-speed centrifugal cleaning by using ultrapure water and ethanol to obtain a precursor, and calcining for 4h at 1073K in a tubular furnace under the protection of N2 at 278K/min to obtain the hierarchical porous carbon nanosphere.
Step 2: preparation of modified electrode
Weighing 1mg of prepared hierarchical porous carbon nanosphere, dispersing the hierarchical porous carbon nanosphere in 1mL of ultrapure water, performing ultrasonic treatment for 10 minutes to form a uniformly dispersed and stable mixed solution, dropwise coating 5 mu L of the mixed solution on the surface of a glassy carbon electrode, and drying in an infrared drying oven to obtain the hierarchical porous carbon nanosphere modified electrode.
A phosphorus-doped hierarchical porous carbon nanosphere modified electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, a reference electrode is a saturated calomel electrode to form a traditional three-electrode system, a phosphate buffer solution is used as an electrolyte solution, the pH value of the phosphate buffer solution is 2, and the concentration of the phosphate buffer solution is 0.1M. The content of luteolin and baicalin in the solution is measured by using a differential pulse voltammetry method.
As shown in fig. 1A, although the prepared hierarchical porous carbon nanosphere has a hierarchical porous structure with coexisting micropores, mesopores and macropores, which is superior to that of a bare electrode in peak response current to luteolin and baicalin, the absence of phosphoric acid activation treatment, the absence of high specific surface area and phosphorus doping, the small contact area of the electrode surface and the absence of active sites make the hierarchical porous carbon nanosphere modified electrode have weaker electrocatalytic activity, and the peak response current is smaller than that of the phosphorus-doped carbon nanosphere modified electrode. The phosphorus-doped hierarchical porous carbon nanosphere modified electrode simultaneously realizes the distinguishable determination of luteolin and baicalin, when a phosphate buffer solution (0.1M, pH 2) simultaneously containing 6 mu M of luteolin and baicalin is used and Differential Pulse Voltammetry (DPV) is used, as shown in figure 1A compared with a bare electrode, the modified electrode initially realizes the distinguishable detection by the obvious response current of the luteolin and the baicalin at 0.55V and 0.45V respectively, but has smaller mutual interference.
Example 3
An electrochemical sensing method capable of simultaneously distinguishing and detecting two flavonoid compounds luteolin and baicalin comprises the following steps:
step 1: preparation of the modifying Material
1g of xylan (95%), 0.3g of polyvinylpyrrolidone and 1mL of sulfuric acid were dissolved in 60mL of ultrapure water, and after ultrasonic dissolution, the resulting solution was transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene and subjected to hydrothermal treatment at 433K for 4 hours. Naturally cooling to room temperature, filtering the obtained brown mixture to remove impurities, repeatedly carrying out high-speed centrifugal cleaning by using ultrapure water and ethanol to obtain a precursor, and drying in a 343K oven. And then, performing phosphoric acid activation treatment (the mass ratio is phosphoric acid (85%): precursor is 4:1), putting the mixture into an oven, drying the mixture at 373K, and finally calcining the mixture at 1073K for 4h at 278K/min in a tubular furnace under the protection of N2 to obtain the phosphorus-doped hierarchical porous carbon nanosphere.
Step 2: preparation of modified electrode
Weighing 1mg of prepared phosphorus-doped hierarchical porous carbon nanosphere, dispersing the phosphorus-doped hierarchical porous carbon nanosphere in 1mL of ultrapure water, performing ultrasonic treatment for 10 minutes to form a uniformly dispersed and stable mixed solution, dropwise coating 5 mu L of the mixed solution on the surface of a glassy carbon electrode, and drying the glassy carbon electrode in an infrared drying oven to obtain the phosphorus-doped hierarchical porous carbon nanosphere modified electrode.
A phosphorus-doped hierarchical porous carbon nanosphere modified electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, a reference electrode is a saturated calomel electrode to form a traditional three-electrode system, a phosphate buffer solution is used as an electrolyte solution, the pH value of the phosphate buffer solution is 2, and the concentration of the phosphate buffer solution is 0.1M. The content of luteolin and baicalin in the solution is measured by using a differential pulse voltammetry method.
As shown in fig. 2, the prepared carbon spheres have a hierarchical porous structure and a nano-scale in which micropores, mesopores, and macropores coexist, and phosphoric acid activation generates a large number of micropores to increase a specific surface area and achieve phosphorus doping. As shown in fig. 1A, the phosphorus-doped hierarchical porous carbon nanosphere modified electrode shows that the maximum peak response current of luteolin and baicalin is better than that of a bare electrode, and the hierarchical porous carbon nanosphere modified electrode and the phosphorus-doped carbon nanosphere modified electrode show that the phosphorus-doped hierarchical porous carbon nanosphere modified electrode has excellent electrocatalytic performance.
Example 4
An electrochemical sensing method capable of simultaneously distinguishing and detecting two flavonoid compounds luteolin and baicalin comprises the following steps:
the preparation method of the modified material and the modified electrode is the same as that of example 3.
A phosphorus-doped hierarchical porous carbon nanosphere modified electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, a reference electrode is a saturated calomel electrode to form a traditional three-electrode system, a phosphate buffer solution is used as an electrolyte solution, the pH value of the phosphate buffer solution is 2, and the concentration of the phosphate buffer solution is 0.1M. The content of luteolin and baicalin in the solution is measured by using a differential pulse voltammetry method, and the obtained data is subjected to first derivative voltammetry treatment, so that the problem that certain interference exists when the peak positions of two flavonoid compounds are too close is solved.
When the first derivative voltammetry is used, as shown in fig. 1B, the peak distance between luteolin and baicalin is wider, and better peak sharpness is obtained, which shows that the modified electrode has excellent electrocatalytic activity on luteolin and baicalin, and the first derivative voltammetry eliminates or reduces the interference of background current and noise, so that the distinguishable detection of luteolin and baicalin is realized.
The oxidase sensor can be used for selectively measuring luteolin and baicalin as shown in FIGS. 3A-B and D-E: luteolin and baicalin with different concentrations are respectively added into a phosphate buffer solution (0.1M, pH is 2), a prepared modified electrode is used, DPV is utilized to selectively measure luteolin or baicalin, one of substances to be detected is stabilized, a response current begins to present a linear relation along with the increase of the concentration of the other substance to be detected, when the concentration is continuously increased, the response current gradually shifts linearly and tends to be gentle, and the reciprocal of the concentration and the reciprocal of the response peak current present a linear relation, which indicates that the prepared sensor has oxidase-like characteristics. In addition, simultaneous detection of luteolin and baicalin by the sensor is shown in fig. 3G-H: luteolin and baicalin with different concentrations are added into a phosphate buffer solution (0.1M, pH is 2) at the same time, DPV is used for simultaneously measuring luteolin and baicalin, the response current begins to show a linear relation along with the increase of the concentration, when the concentration is continuously increased, the response current gradually shifts linearly and slowly becomes gentle, and the reciprocal of the concentration and the reciprocal of the response peak current also show a linear relation, thereby further indicating that the prepared sensor has oxidase-like characteristics. The sensor has wide detection range (0.01-1 μ M), high sensitivity and low detection limit (0.38nM and 2.16nM) for luteolin and baicalin, respectively.
The first derivative voltammetry can process the voltammetry curve, eliminate or reduce the interference of background current and noise, improve the sensitivity of signals which are usually referenced by the slope of a linear equation, and improve the peak resolution of overlapping voltammetry spectra when luteolin and baicalin are detected simultaneously. Compared to the DPV voltammogram (fig. 3A, D, G), the first derivative voltammogram shape is more distinguishable for the characteristic peaks of the two flavonoids by having a very sharp, sharp and narrow peak shape (fig. 4A, C and E). Stabilizing the concentration of one of the flavones, and determining the concentration of the other flavone by using the modified electrode, wherein the slopes of the two flavonoids change relatively little when a first derivative linear relation equation (shown in figures 3C and F) or a traditional voltammetry normal linear equation (shown in figures 4B and D) is used; when two flavonoid compounds are simultaneously measured, the mutual deviation of the slopes of the two flavonoid compounds obtained by the conventional voltammetry normal linear equation is large (figure 3I), and the mutual deviation of the slopes obtained by using the first-order derivative linear relation equation is obviously reduced (figure 4F), so that the interference of background current and noise is eliminated or reduced by the first-order derivative voltammetry, the sensitivity and the peak resolution are improved, and the differential detection of luteolin and baicalin is realized.
As for the performance evaluation of the sensor for simultaneously detecting luteolin and baicalin, as shown in FIGS. 4A-B, the prepared sensor has strong anti-interference performance to luteolin and baicalin, moreover, substances such as different saccharides (sucrose and glucose), amino acids (L-cysteine and citric acid), flavonoids (rutin, arbutin and quercetin), phenols (catechin, p-aminophenol and p-acetaminophen), pesticides (carbendazim), antibiotics (chloramphenicol), vitamins (ascorbic acid and pyridoxine), purine metabolites (uric acid), nerve conduction substances (dopamine hydrochloride) and phytohormones (trans-zeatin, kinetin, abscisic acid and indole-3-acetic acid) are added, the electrochemical response is not obvious, and the error rate of response current in the presence of interferents is less than 5%.
For stability evaluation of the sensor for simultaneous detection of luteolin and baicalin, the modified electrode was continuously subjected to 50 cycles of detection of luteolin and baicalin in a phosphate buffer solution (0.1M, pH 2) containing 6 μ M of luteolin and baicalin at the same time using the above-described DPV detection method. As can be seen from the results in fig. 5, the electrochemical sensor prepared according to the present invention has good stability.
Luteolin and baicalin in human blood samples were measured using the prepared sensors, and the results of the assay are shown in table 1, and human blood samples were diluted 100-fold with phosphate buffered saline (0.1M, pH 2). In human blood samples containing fixed concentrations (2, 4 and 6 μ M) of either luteolin or baicalin alone and in the presence of both flavonoids in phosphate buffered saline (0.1M, pH 2) each concentration was repeated 3 times. When two flavonoids compounds are separately detected, the average recovery rates of luteolin and baicalin in the traditional voltammetry are respectively 99.45-103.98% and 97.83-100.64%, and the RSD is respectively 0.33-1.16% and 0.87-4.83%; the average recovery rates of the first derivative voltammetry are respectively 99.81-103.85% and 97.82-101.07%, and the RSD is respectively 0.29-1.04% and 0.81-3.88%. When luteolin and baicalin are detected simultaneously, the average recovery rate of the traditional voltammetry is 97.78% -104.21% and 98.42% -102.42% respectively, and the RSD is 1.12% -5.60% and 2.09% -6.38% respectively; and the corresponding first-order derivative voltammetry has the average sample-adding recovery rates of luteolin and baicalin of 96.69-100.27% and 95.67-99.95% respectively, and the RSD of 0.88-1.25% and 0.62-2.08% respectively, so that the first-order derivative voltammetry has better results, and simultaneously shows that the constructed oxidase-like sensor has feasibility and practicability when being used for detecting and analyzing actual samples.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. An electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin is characterized in that: the method comprises the steps of taking a phosphorus-doped hierarchical porous carbon nanosphere modified electrode as a working electrode, measuring the content of luteolin and baicalin in a solution by using a differential pulse voltammetry method, and carrying out first-order derivative voltammetry treatment on obtained data.
2. The electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin according to claim 1, which is characterized in that: the method comprises the following steps:
step 1: preparation of the modifying Material
The preparation method comprises the steps of taking xylan with a certain mass as a carbon source, introducing polyvinylpyrrolidone with a certain mass and sulfuric acid with a certain volume, carrying out hydrothermal reaction for a certain time at a certain temperature to obtain a precursor, carrying out centrifugal cleaning with ethanol and water to obtain the precursor, activating the dried precursor and phosphoric acid according to a certain proportion, and finally calcining in a tubular furnace under the protection of inert gas to prepare the phosphorus-doped hierarchical porous carbon nanospheres.
Step 2: preparation of modified electrode
After the phosphorus-doped hierarchical porous carbon nanospheres and ultrapure water are subjected to ultrasonic dispersion according to the proportion of 1mg/mL, 5 mu L of dispersion liquid is dripped on the glassy carbon electrode and dried to prepare the phosphorus-doped hierarchical porous carbon nanosphere modified electrode.
3. The electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin according to claim 2, wherein: in the step 1, the mass of xylan is 1g, the mass of polyvinylpyrrolidone is 0.3g, the volume of sulfuric acid is 1mL, and the concentration of xylan is 95%.
4. The electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin according to claim 2, wherein: in the step 1, the hydrothermal reaction temperature is 433K, and the reaction time is 4 h.
5. The electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin according to claim 2, wherein: in the step 1, the ratio of the precursor to the phosphoric acid is 1:4, and the inert gas is N2。
6. The electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin according to claim 2, wherein: in the step 2, a traditional three-electrode system is formed by taking a phosphorus-doped hierarchical porous carbon nanosphere modified electrode as a working electrode, a platinum wire electrode as a counter electrode and a reference electrode as a saturated calomel electrode, and a phosphate buffer solution is taken as an electrolyte solution.
7. The electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin according to claim 2, wherein: in the step 2, the pH of the phosphate buffer solution is 2, and the concentration is 0.1M.
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