CN115015362B - Electrochemical method for detecting myricetin - Google Patents
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- IKMDFBPHZNJCSN-UHFFFAOYSA-N Myricetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC(O)=C(O)C(O)=C1 IKMDFBPHZNJCSN-UHFFFAOYSA-N 0.000 title claims abstract description 84
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- 229940116852 myricetin Drugs 0.000 title claims abstract description 84
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- 238000002848 electrochemical method Methods 0.000 title claims abstract description 17
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- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000001903 differential pulse voltammetry Methods 0.000 claims description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 239000005662 Paraffin oil Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
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- NJACTCWYYAPTNF-UHFFFAOYSA-N OC=1C(OC=2C=1C(C(=CC=2O)O)=O)C1=CC(=C(C(=C1)O)O)O Chemical compound OC=1C(OC=2C=1C(C(=CC=2O)O)=O)C1=CC(=C(C(=C1)O)O)O NJACTCWYYAPTNF-UHFFFAOYSA-N 0.000 description 1
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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Abstract
The invention discloses an electrochemical method for detecting myricetin, which comprises the following operation steps: (1) synthesis of an aluminum-based metal organic framework CAU-1; (2) Preparing a CAU-1 modified carbon paste electrode to obtain the CAU-1 modified carbon paste electrode; (3) preparing a standard solution; (4) Drawing a standard curve, taking the measured oxidation peak current value of 0.28+/-0.02V into the obtained linear equation, and calculating the content of myricetin in the sample to be measured. The method adopts the carbon paste electrode as the substrate, and the CAU-1 is firstly applied to the preparation of the myricetin electrochemical sensor, so that the sensor is convenient and quick to manufacture, easy to update on the surface, high in sensitivity, good in stability and low in cost.
Description
Technical Field
The invention belongs to the technical field of electrochemical detection methods, and particularly relates to an electrochemical method for detecting myricetin.
Background
Myricetin (3, 5, 7-trihydroxy-2- (3, 4, 5-trihydroxyphenyl) -4H-1-benzofuran-4-one), a flavonoid compound naturally existing in berries, tea, fruits, vegetables and herbs, has pharmacological effects of resisting oxidation, resisting cancer, preventing platelet aggregation, reducing blood glucose and the like, and is widely applied to medicines, foods and health care products. However, it has been reported that myricetin has low bioavailability and poor water solubility, and excessive intake can cause potential risks such as pulmonary fibrosis, so that the establishment of a simple, accurate and high-sensitivity myricetin detection technology has important significance.
The method for measuring myricetin mainly comprises liquid chromatography, spectrophotometry, flow injection chemiluminescence method, electrochemical method, etc. The liquid chromatography is the most commonly used method for measuring the myricetin at present, and has the advantages of high sensitivity, good accuracy and the like, but the pretreatment process is complex, the analysis period is long, and the use and maintenance costs are high. The spectrometry is relatively simple to operate, but has low sensitivity, and is difficult to meet the requirements of actual detection. The electrochemical method has the characteristics of high sensitivity, simple instrument, quick response, low cost, miniaturization realization, easy use and the like, but the currently reported myricetin electrochemical sensor has the defects of complex preparation process, slow surface update and the like, so that the establishment of the myricetin electrochemical sensor with the advantages of simplicity, rapidness and high sensitivity is necessary.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a method for electrochemically detecting myricetin in food based on an aluminum-based metal organic framework CAU-1 material modified carbon paste electrode, and aims to obtain a method with the advantages of simple electrode preparation, high sensitivity, wide linear range and the like.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
an electrochemical method for detecting myricetin, comprising the following operation steps:
(1) Synthesis of aluminum-based metal organic framework CAU-1: aluminum nitrate (Al (NO) 3 ) 3 ) (9.228 g,24.6 mmol) and 2-amino terephthalic acid (H) 2 N-H 2 BDC) (1.492 g,8.2 mmol) is dissolved in methanol and stirred for 1 hour, then transferred into a microwave reaction tube for microwave reaction, after the reaction is finished, the obtained product is centrifuged, the obtained product is respectively washed with water and methanol for 3 times, and the obtained solid is CAU-1 ([ Al) 4 (OH) 2 (OCH 3 ) 4 (H 2 N-BDC) 3 ]·xH 2 O), activating the CAU-1, and cooling for standby;
(2) Preparation of CAU-1 modified carbon paste electrode: placing the CAU-1 prepared in the step (1) and graphite powder into an agate mortar, fully grinding and uniformly mixing, then adding paraffin oil according to the proportion of 1.0g to 0.1mL, namely adding 0.1mL of paraffin oil into the material obtained after 1.0g of CAU-1 and graphite powder are mixed, grinding into uniform paste, pressing the uniform paste into a carbon paste electrode tube shell connected with a copper wire, and grinding and polishing in clean weighing paper to obtain a CAU-1 modified carbon paste electrode (CAU-1/CPE);
(3) Preparing a standard solution: accurately weighing myricetin pure product, dissolving with absolute ethanol, diluting, and fixing volume to prepare myricetin mother liquor; respectively measuring myricetin mother solutions with different volumes, adding the myricetin mother solutions into a phosphoric acid buffer solution, and fixing the volume to obtain a series of standard solutions with different concentrations to be measured;
(4) Drawing a standard curve: inserting the three-electrode system into an electrolytic cell containing 10mL of myricetin standard solution, enriching under stirring, carrying out differential pulse voltammetry scanning within the range of 0.0-0.60V, recording an oxidation peak current value of 0.28+/-0.02V, drawing a standard curve according to the corresponding myricetin concentration value, further obtaining a corresponding linear equation, replacing the myricetin standard solution into a sample to be detected, and carrying the oxidation peak current value of 0.28+/-0.02V into the obtained linear equation according to the same operation, and calculating to obtain the myricetin content in the sample to be detected;
the oxidation peak current value and myricetin concentration are in good linear relation within the ranges of 1-10 mug/L and 10-1000 mug/L respectively; the linear equation is i in the range of 1-10 mug/L p =0.2418c+0.2902, linear equation i in the range of 10-1000 μg/L p =0.0518c+3.0313, the correlation coefficient R is 0.996 and 0.999, respectively; wherein i is p The oxidation peak current (mu A) and the concentration (mu g/L) of myricetin are C; the detection limit of the method is as follows: 0.5 mug/L.
Preferably, the ratio of the amount of aluminum nitrate to the amount of 2-aminoterephthalic acid material in step (1) is 3:1.
preferably, in the step (1), the microwave reaction temperature is 125 ℃, the power is 100W, and the reaction time is 45min; the activation was carried out at 200℃for 24 hours.
Preferably, in the step (2), the mass ratio of the CAU-1 to the graphite powder is 0.05:1.
preferably, the phosphate buffer solution in step (3) has a concentration of 0.1mol/L and a pH=3.0.
Preferably, in the step (3), the myricetin pure product is weighed and diluted by absolute ethyl alcohol, and the myricetin pure product is prepared into a myricetin mother solution with the concentration of 1.0mg/mL by constant volume.
Preferably, the three-electrode system in the step (4) is CAU-1 modified carbon paste electrode as a working electrode; the saturated calomel electrode is used as a reference electrode; the platinum wire electrode is a counter electrode.
Preferably, the enrichment time in step (4) is 180s.
The detection object of the method is myricetin in the myrica rubra bark.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method, the carbon paste electrode is used as a substrate, CAU-1 is firstly applied to the preparation of the myricetin electrochemical sensor, the sensor is convenient and quick to manufacture, the surface is easy to update, the sensitivity is high, the stability is good, and the cost is low;
(2) The intensity and stability of a current signal are remarkably improved based on good adsorptivity of CAU-1 to myricetin, and the detection sensitivity of an electrochemical sensor is improved;
(3) The oxidation peak current and the myricetin concentration of the method respectively have good linear relations within the ranges of 1-10 mug/L and 10-1000 mug/L.
Drawings
FIG. 1 is an SEM image of the synthesized CAU-1 of the present invention at a magnification of 1.00. Mu.m.
FIG. 2 is an XRD pattern for the synthesized CAU-1 of the present invention.
FIG. 3 is a graph of DPV of different electrodes in a 100. Mu.g/L myricetin solution; wherein the curve a is a control bare Carbon Paste Electrode (CPE), and the curve b is a CAU-1 modified carbon paste electrode (CAU-1/CPE) prepared by the method.
FIG. 4 is a graph showing the DPV response of the CAU-1 modified carbon paste electrode (CAU-1/CPE) prepared by the invention to record the standard solutions of myricetin with different concentrations; wherein, the curves a to L respectively represent the DPV curves of the electrodes at the concentrations of 1.0, 3.0, 5.0, 7.0, 10, 20, 40, 80, 100, 400, 800 and 1000 mug/L myricetin standard solutions.
FIG. 5 is a standard graph of myricetin concentration (1-10. Mu.g/L) versus peak current for oxidation.
FIG. 6 is a standard graph of myricetin concentration (10-1000. Mu.g/L) versus peak current for oxidation.
Detailed Description
The following detailed description, in conjunction with the accompanying drawings, describes in detail, but it is to be understood that the scope of the invention is not limited to the specific embodiments. The raw materials and reagents used in the examples were commercially available unless otherwise specified. The methanol used in the examples was analytically pure methanol.
Examples electrochemical method for detecting myricetin in food the electrochemical workstation used was the CHI760E type, and the differential pulse voltammetry parameters were set as follows: the potential increase was 4mV, the amplitude was 50mV, and the pulse width was 0.2s.
Example 1
An electrochemical method for detecting myricetin, comprising the following operation steps:
(1) Synthesis of aluminum-based metal organic framework CAU-1: aluminum nitrate (Al (NO) 3 ) 3 ) (9.228 g,24.6 mmol) and 2-amino terephthalic acid (H) 2 N-H 2 BDC) (1.492 g,8.2 mmol) is dissolved in 50mL methanol and stirred for 1 hour, and then transferred into a microwave reaction tube, the power is kept at 100W, the temperature is 125 ℃ for carrying out microwave reaction for 45min, after the reaction is finished, the obtained product is centrifuged for 10min at 8000rpm, the obtained product is respectively washed with water and analytically pure methanol for 3 times, and the obtained solid is CAU-1 ([ Al) 4 (OH) 2 (OCH 3 ) 4 (H 2 N-BDC) 3 ]·xH 2 O), namely an aluminum-based metal organic frame CAU-1, placing the aluminum-based metal organic frame CAU-1 in a muffle furnace, heating to 200 ℃ for activation for 24 hours, and cooling for standby;
(2) Preparation of CAU-1 modified carbon paste electrode: and (3) mixing the CAU-1 prepared in the step (1) with graphite powder according to the mass ratio of 0.05:1 in an agate mortar, fully grinding and uniformly mixing, and then mixing according to the weight ratio of 1.0g: adding paraffin oil (namely, adding paraffin oil of 0.1mL into a substance obtained by mixing CAU-1 of 1.0g with graphite powder) in a proportion of 0.1mL, grinding into uniform paste, pressing the uniform paste into a carbon paste electrode tube shell connected with copper wires, and grinding and polishing in clean weighing paper to obtain a CAU-1 modified carbon paste electrode (CAU-1/CPE); bare Carbon Paste Electrodes (CPEs) were prepared as controls according to the same procedure as described above except that CAU-1 was not added;
(3) Preparing a standard solution: accurately weighing 0.0100g of myricetin pure product, dissolving the myricetin pure product in absolute ethyl alcohol, diluting, and fixing the volume in a 10mL volumetric flask to prepare myricetin mother liquor with the concentration of 1.0 mg/mL; respectively sucking 0.10mL and 1.00mL myricetin mother solution in a 100mL volumetric flask, adding a phosphoric acid buffer solution to a fixed volume to scale, wherein the concentration of the phosphoric acid buffer solution is 0.1mol/L, the pH=3.0, and shaking uniformly to prepare standard myricetin use solutions with the concentrations of 1000 mug/L and 10000 mug/L respectively; respectively sucking 0.10mL,0.30mL,0.50mL,0.70mL,1.00mL,2.00mL,4.00mL,8.00mL and 10.00mL standard use solution of myricetin with the concentration of 1000 mug/L into a 100mL volumetric flask, adding a phosphoric acid buffer solution to fix the volume to a scale, and shaking uniformly to obtain standard solutions to be detected with the concentration of 1.0 mug/L, 3.0 mug/L, 5.0 mug/L, 7.0 mug/L, 10 mug/L, 20 mug/L, 40 mug/L, 80 mug/L and 100 mug/L; respectively sucking standard use solutions of 4.00mL,8.00mL and 10.00mL with concentration of 10000 mug/L into a 100mL volumetric flask, adding a phosphoric acid buffer solution to fix the volume to scale, and shaking uniformly to obtain standard solutions to be detected with concentration of 400 mug/L, 800 mug/L and 1000 mug/L, wherein the concentration of the phosphoric acid buffer solution is 0.1mol/L, and the pH value is=3.0;
(4) Drawing a standard curve: inserting a three-electrode system into an electrolytic cell containing 10mL of myricetin standard solution, wherein the three-electrode system adopts the CAU-1 modified carbon paste electrode (CAU-1/CPE) prepared in the step (2) as a working electrode, adopts a saturated calomel electrode as a reference electrode and adopts a platinum wire electrode as a counter electrode; after enriching for 180s under stirring condition, carrying out differential pulse voltammetry scanning within the range of 0.0-0.60V, recording an oxidation peak current value of 0.28+/-0.02V, drawing a standard curve according to a myricetin concentration value corresponding to the oxidation peak current value, further obtaining a corresponding linear equation, replacing the myricetin standard solution with a sample to be detected, carrying the oxidation peak current value of 0.28+/-0.02V into the obtained linear equation according to the same operation, and calculating to obtain the myricetin content in the sample to be detected;
the oxidation peak current value and myricetin concentration are in good linear relation within the ranges of 1-10 mug/L and 10-1000 mug/L respectively; the linear equation is i in the range of 1-10 mug/L p =0.2418c+0.2902, linear equation i in the range of 10-1000 μg/L p =0.0518c+3.0313, the correlation coefficient R is 0.996 and 0.999, respectively; wherein i is p The oxidation peak current (mu A) and the concentration (mu g/L) of myricetin are C; the detection limit of the method is as follows: 0.5 mug/L.
Determination of the samples:
taking 5.0g of a waxberry bark powder sample in the market, adding 20mL of absolute ethyl alcohol, carrying out ultrasonic extraction for 30min, centrifuging for 5min at 8000rpm, taking supernatant, repeating the steps for 1 time, collecting 2 times of extracting solution, carrying out rotary evaporation until the extracting solution is nearly dry, adding 8mL of absolute ethyl alcohol for dissolution, and then carrying out constant volume with PBS buffer solution (pH 3.0) until 50mL of the extracting solution is reached to obtain a sample to be detected; 1mL of the sample to be tested was added to 9mL of PBS buffer (pH 3.0) and the sample was tested as shown in Table 1.
Electrochemical test is carried out according to the method and the steps of drawing the standard curve, and the corresponding myricetin concentration value is calculated from the standard curve according to the measured current value. And respectively adding a certain amount of myricetin into the sample to be detected, so that the concentration of the myricetin added into the sample is respectively as follows: 0.5000mg/kg;8.5000mg/kg;40.000mg/kg, tested under the same conditions, and its standard recovery was calculated, the results of which are shown in Table 1:
TABLE 1 Myrican content in Myrica rubra bark sample and labeled recovery measurement result
As shown in Table 1, the measurement results of the samples in the method of the invention are consistent with the measurement results of the high performance liquid chromatography, and the standard recovery rates of the method of the invention are respectively 83.8%, 106.7% and 100.8%, which are all above 80%, which indicates that the established method can be used for detecting myricetin in actual samples. The method provides a set of simple, quick, cheap and high-sensitivity detection scheme for measuring the myricetin content in the myricetin barks.
As can be seen from fig. 1, the material has a uniform and ordered grain-like structure; as can be seen from fig. 2, characteristic peaks of CAU-1 appear at 2θ=6.9 ° (011), 9.9 ° (002) and 13.8 ° (022), indicating successful synthesis of CAU-1; can provide basis for the preparation of the sensor.
As can be seen from FIG. 3, the response current of the CAU-1/CPE in the myricetin solution with the concentration of 100 mug/L is obviously greater than that of the CPE, which proves that the CAU-1/CPE of the invention obviously improves the intensity of the catalytic current signal and improves the sensitivity and the stability of the analysis method.
As can be seen from FIG. 4, the response current of CAU-1/CPE increases with increasing myricetin concentration, which can provide a basis for the standard curve of FIGS. 5 and 6.
As can be seen from FIGS. 5 and 6, the concentration of myricetin has a good linear relationship with the response current of CAU-1/CPE, and the myricetin content information can be obtained through the standard curve.
Aluminum-based metal organic framework CAU-1 ([ Al) 4 (OH) 2 (OCH 3 ) 4 (H 2 N-BDC) 3 ]·xH 2 O) is 2-amino terephthalic acid (H) using aluminum as metal ion 2 N-H 2 BDC) is a ligand, and methanol is a high-stability microporous material synthesized by a solvent. CAU-1 has the characteristics of chemical stability, high pore volume, large specific surface area and the like, and becomes an excellent electrode modifier, so that the sensitivity of myricetin in electrochemical detection is improved due to the large specific surface area and the strong enrichment capacity of myricetin. The CAU-1 modified carbon paste electrode is used as a working electrode for electrochemical detection of myricetin for the first time, and the method has the advantages of simple preparation, quick surface update, low cost, easy acquisition and the like.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. An electrochemical method for detecting myricetin, which is characterized by comprising the following operation steps:
(1) Synthesis of aluminum-based metal organic framework CAU-1: dissolving aluminum nitrate and 2-amino terephthalic acid in methanol, stirring, carrying out microwave reaction, centrifuging the obtained product after the reaction is finished, washing the obtained product with water and methanol for times respectively, obtaining solid CAU-1, activating the CAU-1, and cooling for later use;
(2) Preparation of CAU-1 modified carbon paste electrode: grinding and mixing the CAU-1 prepared in the step (1) with graphite powder, adding paraffin oil according to the proportion of 1.0g to 0.1mL, grinding into uniform paste, pressing the uniform paste into a carbon paste electrode tube shell connected with copper wires, and grinding and polishing to obtain the CAU-1 modified carbon paste electrode;
(3) Preparing a standard solution: weighing myricetin pure product, dissolving with ethanol, diluting, and fixing volume to obtain myricetin mother liquor; respectively measuring myricetin mother solutions with different volumes, adding the myricetin mother solutions into a phosphoric acid buffer solution, and fixing the volume to obtain a series of standard solutions with different concentrations to be measured;
(4) Drawing a standard curve: inserting the three-electrode system into an electrolytic cell containing 10mL of myricetin standard solution, enriching under stirring, carrying out differential pulse voltammetry scanning within the range of 0.0-0.60V, recording an oxidation peak current value of 0.28+/-0.02V, drawing a standard curve according to the corresponding myricetin concentration value, further obtaining a corresponding linear equation, replacing the myricetin standard solution into a sample to be detected, and carrying the oxidation peak current value of 0.28+/-0.02V into the obtained linear equation according to the same operation, and calculating to obtain the myricetin content in the sample to be detected;
the oxidation peak current value and myricetin concentration are in good linear relation within the ranges of 1-10 mug/L and 10-1000 mug/L respectively; the linear equation is i in the range of 1-10 mug/L p =0.2418c+0.2902, linear equation i in the range of 10-1000 μg/L p =0.0518c+3.0313, the correlation coefficient R is 0.996 and 0.999, respectively; wherein i is p The oxidation peak current (. Mu.A) and the concentration (. Mu.g/L) of myricetin were shown as C.
2. The electrochemical method for measuring myricetin according to claim 1, wherein: the ratio of the amount of aluminum nitrate to the amount of 2-aminoterephthalic acid in step (1) was 3:1.
3. the electrochemical method for measuring myricetin according to claim 1, wherein: in the step (1), the microwave reaction temperature is 125 ℃, the power is 100W, and the reaction time is 45min; the activation was carried out at 200℃for 24 hours.
4. The electrochemical method for measuring myricetin according to claim 1, wherein: in the step (2), the mass ratio of the CAU-1 to the graphite powder is 0.05:1.
5. the electrochemical method for measuring myricetin according to claim 1, wherein: the phosphate buffer solution concentration in the step (3) was 0.1mol/L, and ph=3.0.
6. The electrochemical method for measuring myricetin according to claim 1, wherein: in the step (3), the pure myricetin is weighed and diluted by ethanol, and the myricetin mother liquor with the concentration of 1.0mg/mL is prepared by constant volume.
7. The electrochemical method for measuring myricetin according to claim 1, wherein: the three-electrode system in the step (4) is CAU-1 modified carbon paste electrode as a working electrode; the saturated calomel electrode is used as a reference electrode; the platinum wire electrode is a counter electrode.
8. The electrochemical method for measuring myricetin according to claim 1, wherein: the enrichment time in the step (4) is 180s.
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